Effect of charcoal doping on the superconducting properties of MgB 2 bulk

NASA Astrophysics Data System (ADS)

Kim, N. K.; Tan, K. S.; Jun, B.-H.; Park, H. W.; Joo, J.; Kim, C.-J.

2008-09-01

The effect of charcoal doping on the superconducting properties of in situ processed MgB 2 bulk samples was investigated. To understand the size effect of the dopant the charcoal powder was attrition milled for 1 h, 3 h and 6 h using ZrO 2 balls. The milled charcoal powders were mixed with magnesium and boron powders to a nominal composition of Mg(B 0.975C 0.025) 2. The Mg(B 0.975C 0.025) 2 compacts were heat-treated at 900 °C for 0.5 h in flowing Ar atmosphere. Magnetic susceptibility for the samples showed that the superconducting transition temperature ( Tc) decreased as the size of the charcoal powder decreased. The critical current density ( Jc) of Mg(B 0.975C 0.025) 2 prepared using large size charcoal powder was lower than that of the undoped MgB 2. However, a crossover of Jc value was observed at high magnetic fields of about 4 T in Mg(B 0.975C 0.025) 2 prepared using small size charcoal powder. Carbon diffusion into the boron site was easier and gave the Jc increase effect when the small size charcoal was used as a dopant.

Cobalt-Doped Perovskite-Type Oxide LaMnO3 as Bifunctional Oxygen Catalysts for Hybrid Lithium-Oxygen Batteries.

PubMed

Liu, Xiao; Gong, Hao; Wang, Tao; Guo, Hu; Song, Li; Xia, Wei; Gao, Bin; Jiang, Zhongyi; Feng, Linfei; He, Jianping

2018-03-02

Perovskite-type oxides based on rare-earth metals containing lanthanum manganate are promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. Perovskite-type LaMnO 3 shows excellent ORR performance, but poor OER activity. To improve the OER performance of LaMnO 3 , the element cobalt is doped into perovskite-type LaMnO 3 through a sol-gel method followed by a calcination process. To assess electrocatalytic activities for the ORR and OER, a series of LaMn 1-x Co x O 3 (x=0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) perovskite oxides were synthesized. The results indicate that the amount of doped cobalt has a significant effect on the catalytic performance of LaMn 1-x Co x O 3 . If x=0.3, LaMn 0.7 Co 0.3 O 3 not only shows a tolerable electrocatalytic activity for the ORR, but also exhibits a great improvement (>200 mV) on the catalytic activity for the OER; this indicates that the doping of cobalt is an effective approach to improve the OER performance of LaMnO 3 . Furthermore, the results demonstrate that LaMn 0.7 Co 0.3 O 3 is a promising cost-effective bifunctional catalyst with high performance in the ORR and OER for application in hybrid Li-O 2 batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficacy of heat generation in CTAB coated Mn doped ZnFe2O4 nanoparticles for magnetic hyperthermia

NASA Astrophysics Data System (ADS)

Raland, R. D.; Borah, J. P.

2017-01-01

Manganese doped Zinc ferrite (Mn-ZnFe2O4, where Mn  =  0%, 3%, 5% and 7%) nanoparticles were synthesized by a simple co-precipitation method. CTAB (cetyltrimethylammonium bromide) was used as a surfactant to inhibitgrowth and agglomeration. In this work, we have discussed on the influence of CTAB and Mn doping in tailoring the structural and magnetic properties of Mn-ZnFe2O4 nanoparticles for the effective application of magnetic hyperthermia. X-ray diffraction (XRD) pattern confirmed the formation of cubic spinel structure of Mn-ZnFe2O4 nanoparticles. Lattice parameter and x-ray densities were obtained from the Rietveld refinement of the XRD pattern. The presence of CTAB as a stabilizing layer adsorbed on the surface of the nanoparticles were confirmed by transmission electron microscope (TEM) and Raman vibrational spectrum. The saturation magnetization showsan increasing trend with Mn addition owing to cationic re-distribution and an increase super-exchange interaction between the two sub-lattices. Superparamagnetic behaviorof Mn-ZnFe2O4 nanoparticles were confirmed by temperature-dependent zero-field-cooling (ZFC) and field-cooling (FC) magnetization curves. The efficiency of induction heating measured by its specific absorption rate (SAR) and intrinsic loss power (ILP) value varies as a function of saturation magnetization. It has been hypothesized that the maximum generation of heat arises from Neel relaxation mechanism. The optimum generation of heat of Mn-ZnFe2O4 nanoparticle is determined by the higher frequency (f  =  337 kHz) range and maximum concentration of Mn doping.

Convenient synthesis of Mn-doped Zn (O,S) nanoparticle photocatalyst for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Susanto Gultom, Noto; Abdullah, Hairus; Kuo, Dong-Hau

2018-04-01

The conversion of 4-nitrophenol as a toxic and waste pollutant to 4-aminophenol as a non-toxic and useful compound by photocatalytic reduction is highly important. In this work, the solid-solution concept by doping was involved to synthesis earth-abundant and green material of Mn-doped Zn(O,S). Zn(O,S) with different Mn doping contents was easily synthesized at low temperature 90°C for 4-NP reduction without using the reducing agent of NaBH4. The Mn-doped Zn(O,S) catalyst exhibited the enhancements in optical and electrochemical properties compared to un-doped Zn(O,S).It was found that 10% Mn-doped Zn(O,S) had the best properties and it could totally reduce 4-NP after 2h photoreactions under low UV illumination. The hydrogen ion was proposed to involve the 4-NP reduction to 4-AP, which is hydrogen ion and electron replaced the oxygen in amino (NO2) group of 4-NP to form the nitro (NH2) group. We alsoproposed the incorporation of Mn in Zn site in the Zn(O,S) host lattice could make the oxygen surface bonding weak for easily forming the oxygen vacancy. The more oxygen vacancy for more hydrogen ion would be generated to consume for 4-NP reduction.

Tetranuclear clusters containing a CrIII-doped MnIII4O2 core: syntheses, structures, and magnetic properties.

PubMed

Ma, Yun-Sheng; Li, Yi-Zhi; Song, You; Zheng, Li-Min

2008-06-02

The oxidation of MnII carboxylates by (NBu4)Cr2O7 in the presence of different phosphonic acids and chelating ligands results in six CrIII-doped tetranuclear manganese clusters formulated [Mn3CrO2(O2CCH3)4(O3PC5H4N)2(bpy)2] (1), [Mn3CrO2(O2CCH3)4(O3PC5H4N)2(phen)2] (2), [Mn3CrO2(O2CPh)4(O3PC5H4NO)2(phen)2] (3), [Mn3CrO2(O2CPh)4(O3PC6H11)2(bpy)2] (4), [Mn 3CrO2(O2CPh)4(O3PC6H11)2(phen) 2] (5), and [Mn3CrO2(O2CCH3)4(O3PC6H11)2(bpy)2] (6). Single-crystal X-ray analyses reveal that all the compounds contain similar [M4O2]8+ cores with the four metal sites arranged in planar topologies. The metal ions within the core are bridged by both carboxylate and phosphonate ligands. Temperature-dependent magnetic measurements show that in all cases dominant antiferromagnetic interactions are propagated between the metal centers. The ac magnetic measurements on compounds 5 and 6 reveal that both the in-phase and the out-of-phase signals are frequency dependent, characteristic of single-molecule magnet behaviors.

Enhance D. C. resistivity of Ba{sub 0.7}Sr{sub 0.3}TiO{sub 3} ceramic by acceptor (Mn) doping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Hakikat, E-mail: sharmahakikat@yahoo.in; Arya, G. S.; Pramar, Kusum

2015-05-15

In the present work, we prepared Ba{sub 0.7}Sr{sub 0.3}TiO{sub 3} and Mn (2 and 3 at % on Ti site) doped Ba{sub 0.7}Sr{sub 0.3}TiO{sub 3} ceramic by sol- gel method. The samples were characterized by X-ray diffraction (XRD). The XRD patterns reveled that Mn ions did not change the perovskite structure of BST (70/30). The dielectric measurements proved that dielectric constant decreased with Mn doping. The dc resistivity was studied by using I-V measurements. The dc resistivity of the BST increased with Mn doping, which suppressed the leakage current.

Variation of the coordination environment and its effect on the white light emission properties in a Mn-doped ZnO-ZnS complex structure.

PubMed

Cheng, Yan; Chen, Rui; Feng, Haifeng; Hao, Weichang; Xu, Huaizhe; Wang, Yu; Li, Jiong

2014-03-14

Mn-doped ZnO-ZnS complex nanocrystals were fabricated through coating of dodecanethiol on Mn-doped ZnO nanocrystals. The relationship between the component of white light emission and the coordination environments of Mn-dopants were experimentally investigated. It was shown that Mn ions mainly formed Mn(3+)O6 octahedra in as prepared Mn-doped ZnO, while the Mn(3+) ions on the surface of ZnO transferred into Mn(2+) ions at the interface between ZnO and ZnS after dodecanethiol coating. The Mn(2+)S4 tetrahedron density and the orange emission intensity increased upon enhancing the dodecanethiol content. These results provide an alternative way to optimize the white emission spectrum from nanocrystals of Mn-doped ZnS-ZnO complex structures through modulation of the coordination environment of Mn ions.

Magnetic properties of transition metal substituted La 0.85Ag 0.15Mn 1-yM yO 3 compounds (M=Co, Cr and Al)

NASA Astrophysics Data System (ADS)

Srivastava, S. K.; Ravi, S.

2009-12-01

In this paper we report a systematic study of Mn-site substitution by M=Co, Cr and Al in La 0.85Ag 0.15MnO 3 series to understand the magnetic interactions between Mn and other transition metals. The long-range ferromagnetic (FM) ordering of the parent compound was significantly affected by Mn-site substitution. The measured magnetic properties of Co-doped samples have been explained on the basis of FM interactions in Mn 3+-O-Mn 4+, Co 2+-O-Mn 4+, Co 3+-O-Mn 4+ networks and simultaneous antiferromagnetic (AFM) interactions in Mn 4+-O-Mn 4+, Co 2+-O-Mn 3+ networks. The magnetic properties of Cr-doped compounds could be understood on the basis of double exchange FM interactions in Mn 3+-O 2--Mn 4+ networks and competing AFM in Cr 3+-O-Mn 4+, Mn 4+-O-Mn 4+, Cr 3+-O-Mn 3+ networks. However, it is found that the doping of Al ions play a role of magnetic dilution, without contributing any other competing magnetic interaction. The field variations of magnetization of all the above three series could be analysed by fitting to Brillouin function model and the effective spin contribution for FM has been determined. The measured saturation magnetization has been explained quantitatively.

Tuning the magnetocaloric properties of La0.7Ca0.3MnO3 manganites through Ni-doping

NASA Astrophysics Data System (ADS)

Gómez, A.; Chavarriaga, E.; Supelano, I.; Parra, C. A.; Morán, O.

2018-04-01

The effect of Ni2+ doping on the magnetic and magnetocaloric properties of La0.7Ca0.3MnO3 manganites synthesized via the auto-combustion method is reported. The aim of studying Ni2+-substituted La0.7Ca0.3Mn1 - xNixO3 (x = 0 , 0.02 , 0.07, and 0.1) manganites was to explore the possibility of increasing the operating temperature range for the magnetocaloric effect through tuning of the magnetic transition temperature. X-ray diffraction analysis confirmed the phase purity of the synthesized samples. The substitution of Mn3+ ions by Ni2+ ions in the La0.7Ca0.3MnO3 lattice was also corroborated through this technique. The dependence of the magnetization on the temperature reveals that all the compositions exhibit a well-defined ferromagnetic to paramagnetic transition near the Curie temperature. A systematic decrease in the values of the Curie temperature is clearly observed upon Ni2+ doping. Probably the replacement of Mn3+ by Ni2+ ions in the La0.7Ca0.3MnO3 lattice weakens the Mn3+-O-Mn4+ double exchange interaction, which leads to a decrease in the transition temperature and the magnetic moment in the samples. By using Arrott plots, it was found that the phase transition from ferromagnetic to paramagnetic is second order. The maximum magnetic entropy changes observed for the x = 0 , 0.02 , 0.07, and 0.1 composites was 0.85, 0.77, 0.63, and 0.59 J/kg K, respectively, under a magnetic field of 1.5 T. In general, it was verified that the magnetic entropy change achieved for La0.7Ca0.3Mn1 - xNixO3 manganites synthesized via the auto-combustion method is higher than those reported for other manganites with comparable Ni2+-doping levels synthesized via standard solid state reaction. The addition of Ni2+ increases the value of the relative cooling power as compared to that of the parent compound. The highest value of this parameter (∼60 J/kg) is found for a Ni-doping level of 2% around 230 K in a field of 1.5 T.

Mn 4+ emission in pyrochlore oxides

DOE PAGES

Du, Mao-Hua

2014-08-27

For the existing Mn 4+ activated red phosphors have relatively low emission energies (or long emission wavelengths) and are therefore inefficient for general lighting. Density functional calculations are performed to study Mn 4+ emission in rare-earth hafnate, zirconate, and stannate pyrochlore oxides (RE 2Hf 2O 7, RE 2Zr 2O 7, and RE 2Sn 2O 7). We show how the different sizes of the RE 3+ cation in these pyrochlores affect the local structure of the distorted MnO 6 octahedron, the Mn–O hybridization, and the Mn 4+ emission energy. The Mn 4+ emission energies of many pyrochlores are found to bemore » higher than those currently known for Mn 4+ doped oxides and should be closer to that of Y 2O 3:Eu 3+ (the current commercial red phosphor for fluorescent lighting). The O–Mn–O bond angle distortion in a MnO6 octahedron is shown to play an important role in weakening Mn–O hybridization and consequently increasing the Mn 4+ emission energy. Our result shows that searching for materials that allow significant O–Mn–O bond angle distortion in a MnO 6 octahedron is an effective approach to find new Mn 4+ activated red phosphors with potential to replace the relatively expensive Y 2O 3:Eu 3+ phosphor.« less

Magnetic order and polaron formation in hole-doped LaMnO_3

NASA Astrophysics Data System (ADS)

Terashita, Hirotoshi; Neumeier, John J.; Mitchell, J. F.

2003-03-01

We report the magnetic properties of hole-doped La_1-xCa_xMnO3 (0 <= x <= 0.14). A ferromagnetic saturation moment M_sat develops linearly with Mn^4+ concentration. The slope of M_sat versus Mn^4+ concentration is 27 μ_B/(Mn-ion) per substututed Mn^4+, which is about 3 times larger in magnitude than that of electron-doped CaMnO3 [1]. This result suggests differences in the formation of magnetic polarons of the A-type antiferromagnet LaMnO3 versus that of the G-type antiferromagnet CaMnO_3. Supported by NSF Grant DMR9982834 and the USDOE under contract W-31-109-ENG-38. [1] J. J. Neumeier and J. L. Cohn, Phys. Rev. B 61, 14319 (2000).

Mn-Site Doped CaMnO 3: Creation of the CMR Effect

NASA Astrophysics Data System (ADS)

Raveau, B.; Zhao, Y. M.; Martin, C.; Hervieu, M.; Maignan, A.

2000-01-01

The doping of CaMnO3-δ at Mn sites with pentavalent and hexavalent d0 elements - Nb, Ta, W, Mo - modifies the resistivity behavior of this phase, extending the insulating domain and increasing significantly the resistivity at low temperature as the doping element content increases. The higher valency of the doping element introduces electrons; i.e., Mn3+ species are formed in the Mn4+ matrix. Double exchange phenomena then allow ferromagnetic interactions, by application of external magnetic fields which are similar to those observed for electron-doped manganites Ca1-xLnxMnO3 (x≤0.15), but with smaller magnetic moments. Consequently, this Mn site doping induces CMR properties with resistivity ratios considerably larger than those for CaMnO3-δ.

Enhanced electrochemical properties of F-doped Li2MnSiO4/C for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Chao; Xu, Youlong; Sun, Xiaofei; Zhang, Baofeng; Chen, Yanjun; He, Shengnan

2018-02-01

The Li2MnSiO4 as a novel cathode material for lithium ion batteries, performs high specific capacity, high thermal stability, low cost and etc. However, it suffers from relatively low electronic conductivity and lithium ion diffusion rate. Herein, we successfully introduce fluorine to Li2MnSiO4 (Li2MnSiO4-xFx, x = 0.00, 0.01, 0.03 and 0.05) to overcome these obstacles. The results show that F doping not only enlarges the lattice parameters but also decreases the particle size, synergistically improving the lithium ion diffusion of Li2MnSiO4. Moreover, F doping increase electronic conductivity of Li2MnSiO4/C by inhibiting the formation of C-O bonds in the carbon layers. Meanwhile, F doping improves the crystallinity and stabilizes the crystal structure of Li2MnSiO4. Finally, the Li2MnSiO3.97F0.03/C with the best electrochemical performances delivers the initial specific discharge capacity of 279 mA h g-1 at 25mA g-1 current density from 1.5 V to 4.8 V. Also, it maintains a higher capacity (201 mA h g-1) than F-free Li2MnSiO4 (145 mA h g-1) after 50 cycles.

Atomic-Scale Fingerprint of Mn Dopant at the Surface of Sr3(Ru1−xMnx)2O7

PubMed Central

Li, Guorong; Li, Qing; Pan, Minghu; Hu, Biao; Chen, Chen; Teng, Jing; Diao, Zhenyu; Zhang, Jiandi; Jin, Rongying; Plummer, E. W.

2013-01-01

Chemical doping in materials is known to give rise to emergent phenomena. These phenomena are extremely difficult to predict a priori, because electron-electron interactions are entangled with local environment of assembled atoms. Scanning tunneling microscopy and low energy electron diffraction are combined to investigate how the local electronic structure is correlated with lattice distortion on the surface of Sr3(Ru1−xMnx)2O7, which has double-layer building blocks formed by (Ru/Mn)O6 octahedra with rotational distortion. The presence of doping-dependent tilt distortion of (Ru/Mn)O6 octahedra at the surface results in a C2v broken symmetry in contrast with the bulk C4v counterpart. It also enables us to observe two Mn sites associated with the octahedral rotation in the bulk through the “chirality” of local electronic density of states surrounding Mn, which is randomly distributed. These results serve as fingerprint of chemical doping on the atomic scale. PMID:24108411

Silver-doped manganese dioxide and trioxide nanoparticles inhibit both gram positive and gram negative pathogenic bacteria.

PubMed

Kunkalekar, R K; Prabhu, M S; Naik, M M; Salker, A V

2014-01-01

Palladium, ruthenium and silver-doped MnO2 and silver doped Mn2O3 nanoparticles were synthesized by simple co-precipitation technique. SEM-TEM analysis revealed the nano-size of these synthesized samples. XPS data illustrates that Mn is present in 4+ and 3+ oxidation states in MnO2 and Mn2O3 respectively. Thermal analysis gave significant evidence for the phase changes with increasing temperature. Antibacterial activity of these synthesized nanoparticles on three Gram positive bacterial cultures (Staphylococcus aureus ATCC 6538, Streptococcus epidermis ATCC 12228, Bacillus subtilis ATCC 6633) and three Gram negative cultures (Escherichia coli ATCC 8739, Salmonella abony NCTC 6017 and Klebsiella pneumoniae ATCC 1003) was investigated using a disc diffusion method and live/dead assay. Only Ag-doped MnO2 and Ag-doped Mn2O3 nanoparticles showed antibacterial property against all six-test bacteria but Ag-doped MnO2 was found to be more effective than Ag-doped Mn2O3. Copyright © 2013 Elsevier B.V. All rights reserved.

Colossal permittivity and the polarization mechanism of (Mg, Mn) co-doped LaGaO3 ceramics

NASA Astrophysics Data System (ADS)

Luo, Tingting; Liu, Zhifu; Zhang, Faqiang; Li, Yongxiang

2018-03-01

Mg and Mn co-doped LaGa0.7-xMgxMn0.3O3 (x = 0, 0.05, 0.10, 0.15) ceramics were prepared by a solid-state reaction method. The electrical properties of the LaGa0.7-xMgxMn0.3O3 ceramics were studied in detail by dielectric spectra, impedance spectra, and I-V characteristic analysis. Colossal permittivity up to 104 could be obtained across the frequency range up to 104 Hz. The impedance analysis of the co-doped LaGaO3 ceramics indicated that the Mott's variable range hopping (VRH) polarization should be the main origin of colossal permittivity. Mg and Mn co-doping suppressed the formation of Mn3+ and enhanced the VRH polarization, resulting in increased permittivity. Partial localization of electrons by Mg reduced the long-range electron hopping and led to the decrease in dielectric loss.

Moessbauer studies in Zn(2+)0.3 Mn(2+)0.7 Mn(3+) (2-y) Fe(3+) (2-y) O4

NASA Technical Reports Server (NTRS)

Gupta, R. G.; Mendiratta, R. G.; Escue, W. T.

1975-01-01

The Mossbauer effect has proven to be effective in the study of nuclear hyperfine interactions. Ferrite systems having the formula (Zn(2+)0.3)(Mn(2+)0.7)(Mn(3+)y)(Fe(3+)2-y)(O4) were prepared and studied. These systems can be interpreted as mangacese-doped zinc and a part of iron ions. A systematic study of these systems is presented to promote an understanding of their microstructure for which various theories were proposed.

Synthesis and electrochemical characterizations of spinel LiMn1.94MO4 (M = Mn0.06, Mg0.06, Si0.06, (Mg0.03Si0.03)) compounds as cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhao, Hongyuan; Liu, Xingquan; Cheng, Cai; Li, Qiang; Zhang, Zheng; Wu, Yue; Chen, Bing; Xiong, Weiqiang

2015-05-01

The spinel LiMn1.94MO4 (M = Mn0.06, Mg0.06, Si0.06, (Mg0.03Si0.03)) compounds are successfully synthesized by citric acid-assisted sol-gel method. The crystal structures and morphologies of synthesized compounds are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. All the compounds possess the cubic spinel structure of LiMn2O4 with space group of Fd-3m. The electrochemical properties of synthesized compounds are investigated by galvanostatic charge-discharge test, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that the Si-doping can increase the discharge capacity of LiMn2O4 due to the more expanded and regular MnO6 octahedra. In particular, for the LiMn1.94Mg0.03Si0.03O4 compound, the addition of Si4+ ions can make up for the shortage of Mg-doping in term of the discharge capacity. As a result, the Mg2+ and Si4+ co-doping has the effect of synergistic enhancement, which can make full use of the respective advantages of Mg-doping and Si-doping. The optimal LiMn1.94Mg0.03Si0.03O4 can deliver the initial discharge capacity of 128.3 mAh g-1 with good capacity retention of 92.8% after 100 cycles at 0.5 C in the voltage range of 3.20-4.35 V. Compared with the undoped LiMn2O4, the co-doped compound also presents superior rate performance, especially the capacity recovery performance.

Hydrothermal synthesis and magnetic properties of Mn doped ZnS nanoparticles

NASA Astrophysics Data System (ADS)

Rashad, M. M.; Rayan, D. A.; El-Barawy, K.

2010-01-01

Nanocrystallite Mn doped Zn1-XS (X = 0 to 0.4) powders have been synthesized through a hydrothermal route. The effect of the hydrothermal temperature and Mn2+ ions substitution on the crystal structure, crystallite size, microstructure and magnetic properties were investigated using (XRD), (SEM) and (VSM). The results revealed that wurtzite zinc sulfide phase was formed using thiourea as a sulfur source at temperature 150- 200oC for 24 h. The crystallite size was (7.9-15.1 nm) was obtained at the same conditions. The doping of Mn2+ ions decreased the crystallite size of the formed ZnS wurtzite phase was in the range between 7.9 and 3.8 nm. SEM micrographs showed that the produced ZnS and Mn doped ZnS particles were appeared as spherical shape. The magnetic properties were improved by substitution of Mn2+ ions up to 0.2.

Luminescence Characteristics of ZnGa2O4 Thick Film Doped with Mn2+ and Cr3+ at Various Sintering Temperatures

NASA Astrophysics Data System (ADS)

Cha, Jae Hyeok; Kim, Kyung Hwan; Park, Yong Seo; Kwon, Sang Jik; Choi, Hyung Wook

2007-10-01

ZnGa2O4 phosphor separately doped with Mn2+ and Cr3+ was synthesized by solid-state reaction, and thick films were deposited by screen printing. The X-ray diffraction (XRD) patterns of ZnGa2O4 phosphor thick films show a (311) main peak and a spinal phase. Uniform distribution and filled morphology of the doped ZnGa2O4 phosphor thick films were formed at the sintering temperature of 1100 °C. The CL spectrum of Mn2+-doped ZnGa2O4 shows the main peak of 512 nm green emission with the 4T1→6A1 transition of Mn2+ ions and the CL spectrum of Cr3+-doped ZnGa2O4 shows the main peak of 716 nm red emission with the 2E→4A2 transition of Cr3+ ions.

Complex doping chemistry owing to Mn incorporation in nanocrystalline anatase TiO2 powders.

PubMed

Guo, Meilan; Gao, Yun; Shao, G

2016-01-28

Mn-doped TiO2 powders with a wide range of nominal doping levels were fabricated using a one-step hydrothermal method followed by 400 °C annealing. Anatase powders with a uniform size distribution below 10 nm were obtained. The maximum solubility of Mn in the TiO2 lattice was around 30%, beyond which the Mn3O4 compound appeared as a secondary phase. The optical absorption edges for Mn-doped anatase TiO2 were red-shifted effectively through increasing Mn content. Alloying chemistry and associated elemental valences were elaborated through combining X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and theoretical simulation in the framework of density functional theory (DFT). The results showed that the Mn species exhibited mixed valence states of 3+ and 4+ in anatase TiO2, with the latter being the key to remarkable photocatalytic performance.

Enhancement of the critical current density and flux pinning of MgB2 superconductor by nanoparticle SiC doping

NASA Astrophysics Data System (ADS)

Dou, S. X.; Soltanian, S.; Horvat, J.; Wang, X. L.; Zhou, S. H.; Ionescu, M.; Liu, H. K.; Munroe, P.; Tomsic, M.

2002-10-01

Doping of MgB2 by nano-SiC and its potential for the improvement of flux pinning were studied for MgB2-x)(SiCx/2 with x=0, 0.2, and 0.3 and for 10 wt % nano-SiC-doped MgB2 samples. Cosubstitution of B by Si and C counterbalanced the effects of single-element doping, decreasing Tc by only 1.5 K, introducing intragrain pinning centers effective at high fields and temperatures, and significantly enhancing Jc and Hirr. Compared to the undoped sample, Jc for the 10 wt % doped sample increased by a factor of 32 at 5 K and 8 T, 42 at 20 K and 5 T, and 14 at 30 K and 2 T. At 20 K and 2 T, the Jc for the doped sample was 2.4 x105 A/cm2, which is comparable to Jc values for the best Ag/Bi-2223 tapes. At 20 K and 4 T, Jc was twice as high as for the best MgB2 thin films and an order of magnitude higher than for the best Fe/MgB2 tapes. The magnetic Jc is consistent with the transport Jc which remains at 20 000 A/cm2 even at 10 T and 5 K for the doped sample, an order of magnitude higher than the undoped one. Because of such high performance, it is anticipated that the future MgB2 conductors will be made using a formula of MgBxSiyCz instead of pure MgB2.

Influence of film thickness and Fe doping on LPG sensing properties of Mn3O4 thin film grown by SILAR method

NASA Astrophysics Data System (ADS)

Belkhedkar, M. R.; Ubale, A. U.

2018-05-01

Nanocrystalline Fe doped and undoped Mn3O4 thin films have been deposited by Successive Ionic Layer Adsorption and Reaction (SILAR) method onto glass substrates using MnCl2 and NaOH as cationic and anionic precursors. The grazing incidence X-ray diffraction (GIXRD) and field emission scanning electron microscopy (FESEM)) have been carried out to analyze structural and surface morphological properties of the films. The LPG sensing performance of Mn3O4thin films have been studied by varying temperature, concentration of LPG, thickness of the film and doping percentage of Fe. The LPG response of the Mn3O4thin films were found to be enhances with film thickness and decreases with increased Fe doping (0 to 8 wt. %) at 573 K temperature.

Facile hydrothermal synthesis of mn doped ZnO nanopencils for development of amperometric glucose biosensors

NASA Astrophysics Data System (ADS)

Shukla, Mayoorika; Pramila; Agrawal, Jitesh; Dixit, Tejendra; Palani, I. A.; Singh, Vipul

2018-05-01

Mn doped ZnO nanopencils were synthesized via low temperature hydrothermal process for fabrication of enzymatic electrochemical glucose biosensor. The KMnO4 was found to play a dual role in modifying morphology and inducing Mn doping. Interestingly, two different types of morphologies viz nanorods and nanopencils along with Mn doping in the later were obtained. Incorporation of Mn has shown a tremendous effect on the morphological variations, repression of defects and electrochemical charge transfer at electrode electrolyte interface. The possible reason behind obtained morphological changes has been proposed which in turn were responsible for the improvement in the different figure of merits of as fabricated enzymatic electrochemical biosensor. There has been a 17 fold enhancement in the sensitivity of the as fabricated glucose biosensor from ZnO nanorods to Mn doped ZnO nanopencils which can be attributed to morphological variation and Mn doping.

Observation of ferromagnetism in Mn doped KNbO3

NASA Astrophysics Data System (ADS)

Manikandan, M.; Venkateswaran, C.

2015-06-01

Pure and Mn doped KNbO3 have been prepared by ball milling assisted ceramic method. Mn ion had been doped at Nb site to induce ferromagnetism at room temperature. X-ray diffraction (XRD) patterns reveal the formation of orthorhombic phase. High resolution scanning electron micrograph (HR-SEM) of both pure and Mn doped samples show a mixture of spherical and plate like particles. Room temperature magnetic behavior of both the samples were analyzed using vibrating sample magnetometer (VSM). 5% Mn doped KNbO3 exhibits ferromagnetic behavior. Observed ferromagnetic feature has been explained by interactions between bound magnetic polarons which are created by Mn4+ ions.

Co-current Doping Effect of Nanoscale Carbon and Aluminum Nitride on Critical Current Density and Flux Pinning Properties of Bulk MgB2 Superconductors

NASA Astrophysics Data System (ADS)

Tripathi, D.; Dey, T. K.

2018-05-01

The effect of nanoscale aluminum nitride (n-AlN) and carbon (n-C) co-doping on superconducting properties of polycrystalline bulk MgB2 superconductor has been investigated. Polycrystalline pellets of MgB2, MgB2 + 0.5 wt% AlN (nano), MgB_{1.99}C_{0.01} and MgB_{1.99}C_{0.01} + 0.5 wt% AlN (nano) have been synthesized by a solid reaction process under inert atmosphere. The transition temperature (TC) estimated from resistivity measurement indicates only a small decrease for C (nano) and co-doped MgB2 samples. The magnetic field response of investigated samples has been measured at 4, 10, and 20 K in the field range ± 6 T. MgB2 pellets co-doped with 0.5 wt% n-AlN and 1 wt% n-C display appreciable enhancement in critical current density (J_C) of MgB2 in both low (≥ 3 times), as well as, high-field region (≥ 15 times). J_C versus H behavior of both pristine and doped MgB2 pellets is well explained in the light of the collective pinning model. Further, the normalized pinning force density f_p(= F_p/F_{pmax}) displays a fair correspondence with the scaling procedure proposed by Eisterer et al. Moreover, the scaled data of the pinning force density (i.e., f_p{-}h data) of the investigated pellets at different temperature are well interpreted by a modified Dew-Hughes expression reported by Sandu and Chee.

A new type of glucose biosensor based on surface acoustic wave resonator using Mn-doped ZnO multilayer structure.

PubMed

Luo, Jingting; Luo, Pingxiang; Xie, Min; Du, Ke; Zhao, Bixia; Pan, Feng; Fan, Ping; Zeng, Fei; Zhang, Dongping; Zheng, Zhuanghao; Liang, Guangxing

2013-11-15

This work reports a high-performance Mn-doped ZnO multilayer structure Love mode surface acoustic wave (SAW) biosensor for the detection of blood sugar. The biosensor was functionalized via immobilizing glucose oxidase onto a pH-sensitive polymer which was attached on Mn-doped ZnO biosensor. The fabricated SAW glucose biosensor is highly sensitive, accurate and fast with good anti-interference. The sensitivity of the SAW glucose biosensor is 7.184 MHz/mM and the accuracy is 6.96 × 10(-3)mM, which is sensitive and accurate enough for glucose monitoring. A good degree of reversibility and stability of the glucose sensor is also demonstrated, which keeps a constant differential frequency shift up to 32 days. Concerning the time response to human serum, the glucose sensor shows a value of 4.6 ± 0.4 min when increasing glucose concentrations and 7.1 ± 0.6 min when decreasing, which is less than 10 min and reach the fast response requirement for medical applications. The Mn-doped ZnO Love mode SAW biosensor can be fully integrated with CMOS Si chips and developed as a portable, passive and wireless real time detection system for blood sugar monitoring in human serum. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrical and magnetic properties of several ruthenates and superconductivity in magnesium boride and MgCNi(3)

NASA Astrophysics Data System (ADS)

He, Tao

2002-09-01

Perovskite-based ruthenates have been receiving considerable attention both because of their interesting and variable magnetic properties, and because of the discovery of exotic superconductivity in the layered ruthenate Sr 2RuO4. Another perovskite, SrRuO3, is the only known oxide ferromagnet with a 4d transition metal, and magnetism is easily suppressed by Ca doping. The suppression of ferromagnetic interactions in SrxCa1-xRuO3 has frequently been attributed to the orthorhombic structural distortion, either through the crossover to classical antiferromagnetic interactions, or, alternatively, to a nearly ferromagnetic metal. This study reports the comparison of the magnetic properties of Srx(Na0.5La0.5)1-xRuO 3 to SrxCa1-xRuO3, showing that there is a much faster suppression of ferromagnetic interactions in the former case. Neither orthorhombic distortion nor cation size disorder can explain the observed difference. Instead, the difference may be attributed to charge disorder on the A-site, which greatly affects the local environment of Ru atoms and leads to the faster suppression of the long-range ferromagnetic state. The magnetic ground state of perovskite structure CaRuO3 has been enigmatic for decades. This study also shows that paramagnetic CaRuO 3 can be made ferromagnetic by very small amounts of partial substitution of Ru by various transition metals. The results are consistent with the recent proposal that CaRuO3 is not a classical antiferromagnet, but rather is poised at a critical point between ferromagnetic and paramagnetic ground states. Ti, Fe, Mn and Ni doping result in ferromagnetic behavior. The second part of this thesis is on the superconductivity of MgB 2 and MgCNi3. Since the discovery of superconductivity in MgB2 in January 2001, detailed information on its properties has been rapidly accumulated. The reported properties, the very simple structure, and the commercial availability of this material make MgB2 a favorite candidate for large scale and electronic applications. In thin film fabrication, the reactivity of MgB2 with substrate materials or insulating or metallic layers in multi-layer circuits is an important factor. In this work the reactivity of MgB2 with powdered forms of common substrate and electronic materials is studied. Some oxides and nitrides prove to be potentially good substrates for making thin films, while others, including some commonly used substrates like Al2O3, SrTiO 3, and SiO2, have serious chemical compatibility problems. In the latter case, caution should be taken when fabricating thin films. This thesis also describes the discovery of superconductivity at 8 K in the perovskite structure compound MgCNi3. This material is the three-dimensional analogue of the LnNi2B2C family of superconductors, which have Tcs up to 16K. The itinerant electrons in both LnNi2B2C and MgCNi3 are based on partial filling of Ni d-states, which generally leads to ferromagnetism, as is the case in metallic Ni. The very high relative proportion of Ni in MgCNi3 is especially suggestive of the possible importance of magnetic interactions in the superconductivity, and, further, the lower Tc of the three-dimensional compound is contrary to conventional ideas.

Exploring the Cr{sup 2+} doping effect on structural, vibrational and dielectric properties of Mn-Zn ferrites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, Pankaj; Dar, M. A.; Varshney, Dinesh, E-mail: vdinesh33@rediffmail.com, E-mail: ty.ru123@gmail.com

2016-05-23

A series of Cr doped Mn-Zn ferrites with compositional formula Mn{sub 0.5}Zn{sub 0.5-x}Cr{sub x}Fe{sub 2}O{sub 4} (x = 0, 0.3, 0.5) were prepared by solid-state reaction route. X-ray diffraction (XRD) analysis reveals that the samples prepared are polycrystalline cubic spinel in structure (Fd3m) with some secondary phase of α–Fe{sub 2}O{sub 3}. Slight variation in the lattice parameter of Cr doped Mn{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} has been observed due to difference in ionic radii of cations. Small shift in Raman modes towards higher wave number has been observed. Further the line width decreases with the doping ions. A giant dielectricmore » constant ~10{sup 4} is observed for parent Mn{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} which is found to decrease with increase in Cr{sup 2+} doping. Low dielectric loss is observed for Mn{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} and improves with Cr{sup 2+} doping at Zn{sup 2+} site.« less

Understanding the effects of cationic dopants on α-MnO 2 oxygen reduction reaction electrocatalysis

DOE PAGES

Lambert, Timothy N.; Vigil, Julian A.; White, Suzanne E.; ...

2017-01-09

Nickel-doped α-MnO 2 nanowires (Ni–α-MnO 2) were prepared with 3.4% or 4.9% Ni using a hydrothermal method. A comparison of the electrocatalytic data for the oxygen reduction reaction (ORR) in alkaline electrolyte versus that obtained with α-MnO 2 or Cu–α-MnO 2 is provided. In general, Ni-α-MnO 2 (e.g., Ni-4.9%) had higher n values (n = 3.6), faster kinetics (k = 0.015 cm s –1), and lower charge transfer resistance (R CT = 2264 Ω at half-wave) values than MnO 2 (n = 3.0, k = 0.006 cm s –1, R CT = 6104 Ω at half-wave) or Cu–α-MnO 2 (Cu-2.9%,more » n = 3.5, k = 0.015 cm s –1, R CT = 3412 Ω at half-wave), and the overall activity for Ni–α-MnO 2 trended with increasing Ni content, i.e., Ni-4.9% > Ni-3.4%. As observed for Cu–α-MnO 2, the increase in ORR activity correlates with the amount of Mn 3+ at the surface of the Ni–α-MnO 2 nanowire. Examining the activity for both Ni–α-MnO 2 and Cu–α-MnO 2 materials indicates that the Mn 3+ at the surface of the electrocatalysts dictates the activity trends within the overall series. Single nanowire resistance measurements conducted on 47 nanowire devices (15 of α-MnO 2, 16 of Cu–α-MnO 2-2.9%, and 16 of Ni–α-MnO 2-4.9%) demonstrated that Cu-doping leads to a slightly lower resistance value than Ni-doping, although both were considerably improved relative to the undoped α-MnO 2. As a result, the data also suggest that the ORR charge transfer resistance value, as determined by electrochemical impedance spectroscopy, is a better indicator of the cation-doping effect on ORR catalysis than the electrical resistance of the nanowire.« less

The effect of cation doping on spinel LiMn 2O 4: a first-principles investigation

NASA Astrophysics Data System (ADS)

Shi, Siqi; Ouyang, Chuying; Wang, Ding-sheng; Chen, Liquan; Huang, Xuejie

2003-05-01

The effect of the cation doping on the electronic structure of spinel LiM yMn 2- yO 4 (M=Cr, Mn, Fe, Co and Ni) has been calculated by first-principles. Our calculation shows that new M-3d bands emerge in the density of states compared with that in LiMn 2O 4. Simultaneously, the new O-2p bands appear accordingly in almost the same energy range around the Fermi energy owing to the M-3d/O-2p interaction. It is found that the appearance of new O-2p bands in the lower energy position results in a higher intercalation voltage. Consequently, the origin of higher intercalation voltage in LiM yMn 2- yO 4 can be ascribed to the lower O-2p level introduced by the doping cation M.

Synthesis and characterization of single-phase Mn-doped ZnO

NASA Astrophysics Data System (ADS)

Chattopadhyay, S.; Dutta, S.; Banerjee, A.; Jana, D.; Bandyopadhyay, S.; Chattopadhyay, S.; Sarkar, A.

2009-05-01

Different samples of Zn 1-xMn xO series have been prepared using conventional solid-state sintering method. We identified up to what extent doping will enable us to synthesize single-phase polycrystalline Mn-doped ZnO sample, which is one of the prerequisites for dilute magnetic semiconductor, and we have analyzed its some other physical aspects. In synthesizing the samples, proportion of Mn varies from 1 to 5 at%. However, the milling time varied (6, 12, 24, 48 and 96 h) only for 2 at% Mn-doped samples while for other samples (1, 3, 4 and 5 at% Mn doped) the milling time has been fixed to 96 h. Room-temperature X-ray diffraction (XRD) data reveal that all of the prepared samples up to 3 at% of Mn doping exhibit wurtzite-type structure, and no segregation of Mn and/or its oxides has been found. The 4 at% Mn-doped samples show a weak peak of ZnMn 2O 4 apart from the other usual peaks of ZnO and the intensity of this impurity peak has been further increased for 5 at% of Mn doping. So beyond 3 at% doping, single-phase behavior is destroyed. Band gap for all the 2 at% Mn-doped samples has been estimated to be between 3.21 and 3.19 eV and the reason for this low band gap values has been explained through the grain boundary trapping model. The room-temperature resistivity measurement shows an increase of resistivity up to 48 h of milling and with further milling it saturates. The defect state of these samples has been investigated using the positron annihilation lifetime (PAL) spectroscopy technique. Here all the relevant lifetime parameters of positron i.e. free annihilation ( τ1) at defect site ( τ2) and average ( τav) increases with milling time.

Development and characterization of Mn2+-doped MgO nanoparticles by solution combustion synthesis

NASA Astrophysics Data System (ADS)

Basha, Md. Hussain; Gopal, N. O.; Rao, J. L.; Nagabhushana, H.; Nagabhushana, B. M.; Chakradhar, R. P. S.

2015-06-01

Mn doped MgO Nanoparticles have been prepared by Solution Combustion Synthesis. The synthesized sample is characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Electron Paramagnetic Resonance (EPR). The prepared MgO:Mn (1 mol%) nano crystals appear to be of simple cubic crystalline phase with lattice parameters a = 4.218(2) Å and cell volume = 74.98 (7) Å3. SEM micrograph of powders show highly porous, many agglomerates with irregular morphology, large voids, cracks and pores. EPR spectrum of the sample at room temperature exhibit an isotropic sextet hyperfine pattern, centered at g=1.99, characteristic if Mn2+ ions with S=I=5/2.The observed g value and the hyperfine value reveal the ionic bonding between Mn2+ and its surroundings.

The effect of nano-alumina on structural and magnetic properties of MgB2 superconductors

NASA Astrophysics Data System (ADS)

Ansari, Intikhab A.; Shahabuddin, M.; Ziq, Khalil A.; Salem, A. F.; Awana, V. P. S.; Husain, M.; Kishan, H.

2007-08-01

Nano-Al2O3 doped Mg1-xAlxB2 with 0<=x<=6% were synthesized by solid state reaction at 750 °C in Fe tube encapsulation under a vacuum of 10-5 Torr. Resistance measurement shows that the Tc decreases with x and zero resistivity for x = 0 and 6% are obtained at 38 and 35 K, respectively. XRD measurement shows that the lattice parameter and cell volume also decrease monotonically with increasing doping levels. From this we infer that the Al has been substituted in the lattice of MgB2 at Mg sites. Resistivity measurement shows a systematic decrease in Tc with doping which also confirms the substitution of Al. Magnetization studies in the temperature range from 4 to 35 K and in the magnetic field up to 9 T shows a significant increase in the irreversibility field (Hirr), critical current density (Jc) and remanent magnetization (MR) with increasing concentration of the Al2O3 nanoparticle. At low fields we have observed large vortex instabilities (known as a vortex avalanche) associated with all doped samples. The vortex-avalanche effect is reduced with increasing temperature and vanishes near 20 K. The results are discussed in terms of local-vortex instabilities caused by doping of Al2O3 nanoparticles.

Microwave absorption enhancement, magnetic coupling and ab initio electronic structure of monodispersed (Mn1-xCox)3O4 nanoparticles

NASA Astrophysics Data System (ADS)

Zhao, Pengfei; Liang, Chongyun; Gong, Xiwen; Gao, Ran; Liu, Jiwei; Wang, Min; Che, Renchao

2013-08-01

Monodispersed manganese oxide (Mn1-xCox)3O4 (0 <= x <= 0.5) nanoparticles, less than 10 nm size, are respectively synthesized via a facile thermolysis method at a rather low temperature, ranging from 90 to 100 °C, without any inertia gas for protection. The influences of the Co dopant content on the critical reaction temperature required for the nanoparticle formation, electronic band structures, magnetic properties, and the microwave absorption capability of (Mn1-xCox)3O4 are comprehensively investigated by means of both experimental and theoretical approaches including powder X-ray diffraction (XRD), electron energy loss spectroscopy (EELS), super conductivity quantum interference device (SQUID) examination, and first-principle simulations. Co is successfully doped into the Mn atomic sites of the (Mn1-xCox)3O4 lattice, which is further confirmed by EELS data acquired from one individual nanoparticle. Therefore, continuous solid solutions of well-crystallized (Mn1-xCox)3O4 products are achieved without any impurity phase or phase separation. With increases in the Co dopant concentration x from 0 to 0.5, the lattice parameters change systemically, where the overall saturation magnetization at 30 K increases due to the more intense coupling of the 3d electrons between Mn and Co, as revealed by simulations. The microwave absorption properties of the (Mn1-xCox)3O4 nanoparticles are examined between 2 and 18 GHz. The maximum absorption peak -11.0 dB of the x = 0 sample is enhanced to -11.5 dB for x = 0.2, -12.7 dB for x = 0.25, -15.6 dB for x = 0.33, and -24.0 dB for x = 0.5 respectively, suggesting the Co doping effects. Our results might provide novel insights into the understanding of the influences of metallic ion doping on the electromagnetic properties of metallic oxide nanomaterials.Monodispersed manganese oxide (Mn1-xCox)3O4 (0 <= x <= 0.5) nanoparticles, less than 10 nm size, are respectively synthesized via a facile thermolysis method at a rather low temperature, ranging from 90 to 100 °C, without any inertia gas for protection. The influences of the Co dopant content on the critical reaction temperature required for the nanoparticle formation, electronic band structures, magnetic properties, and the microwave absorption capability of (Mn1-xCox)3O4 are comprehensively investigated by means of both experimental and theoretical approaches including powder X-ray diffraction (XRD), electron energy loss spectroscopy (EELS), super conductivity quantum interference device (SQUID) examination, and first-principle simulations. Co is successfully doped into the Mn atomic sites of the (Mn1-xCox)3O4 lattice, which is further confirmed by EELS data acquired from one individual nanoparticle. Therefore, continuous solid solutions of well-crystallized (Mn1-xCox)3O4 products are achieved without any impurity phase or phase separation. With increases in the Co dopant concentration x from 0 to 0.5, the lattice parameters change systemically, where the overall saturation magnetization at 30 K increases due to the more intense coupling of the 3d electrons between Mn and Co, as revealed by simulations. The microwave absorption properties of the (Mn1-xCox)3O4 nanoparticles are examined between 2 and 18 GHz. The maximum absorption peak -11.0 dB of the x = 0 sample is enhanced to -11.5 dB for x = 0.2, -12.7 dB for x = 0.25, -15.6 dB for x = 0.33, and -24.0 dB for x = 0.5 respectively, suggesting the Co doping effects. Our results might provide novel insights into the understanding of the influences of metallic ion doping on the electromagnetic properties of metallic oxide nanomaterials. Electronic supplementary information (ESI) available: Fig. S1. A digital photo showing the large-scale synthesis of our monodispersed (Mn1-xCox)3O4 Fig. S2. Microwave absorption measurements; Fig. S3. Schematic diagram of the microwave absorption mechanism of the (Mn1-xCox)3O4. See DOI: 10.1039/c3nr02287k

Nitrogen-doped carbon coated MnO nanopeapods as superior anode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Ding, Yu; Chen, Lihui; Pan, Pei; Du, Jun; Fu, Zhengbing; Qin, Caiqin; Wang, Feng

2017-11-01

High performance nitrogen-doped carbon (NC) materials decorated with MnO hybrid (MnO@NC) composites with a nanopeapod appearance were synthesized by with a simple hydrothermal method and insuit-polymeric route. As an anode material for lithium ion batteries (LIBs), the nanopeapod structure of MnO@NC composites with internal void spaces exhibits good rate capability, high conductivity and excellent cycling stability. After 200 cycles, the nanopeapod composites yield a specific capacity of 775.4 mAh g-1 at 100 mA g-1 and a high-rate capacity of 559.7 mAh g-1 at 1000 mA g-1. The proposed synthesis of nanopeapod structure composites with an internal room is an efficient design with excellent electrode materials for rechargeable LIBs.

SU-E-T-264: Preliminary Results On New Optically Stimulated Luminescent Materials for Proton Therapy Dosimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doull, B; Zheng, Y; Procure Proton Therapy Center, Oklahoma City, OK

2014-06-01

Purpose: The objective of this work is to test the premise that luminescence materials with less under-response to proton beams can be identified by testing their dose response to low-LET radiation. The goal is to develop new Optically Stimulated Luminescence (OSL) materials with improved response for proton therapy dosimetry. Methods: We first measured the dose response of new OSL materials, synthesized in our laboratory, to low-LET radiation (beta rays from a {sup 90}Sr/{sup 90}Y source) and selected two materials having different OSL saturation characteristics and good dosimetric properties, namely MgB4O7:Ce,Li and MgO:Li. Commercial Al2O3:C was also used for comparison. Thesemore » materials were then irradiated at several depths along a pristine proton beam. The luminescence responses of the materials, relative to the entrance response, were compared with the depth dose profile measured by a multiple-layer ion chamber. Results: The OSL signals of MgB4O7:Ce,Li and MgO:Li were characterized for signal stability, dose response, and response to a clinical proton beam. The materials were also compared with the commercial Al2O3:C. The signals from both MgB4O7:Ce,Li and MgO:Li were relatively stable after a one day delay following irradiation. The low-LET dose response of the materials showed that, over the dose range investigated (up to ∼800 Gy), MgB4O7:Ce,Li did not saturate, whereas MgO:Li and Al2O3:C saturated at doses of ∼100 Gy. MgB4O7:Ce,Li showed less underresponse to proton beams than MgO:Li and Al2O3:C. Conclusion: In general the material with the highest saturation doses for low-LET radiation (MgB4O7:Ce,Li) showed the least under-response to proton beams, which suggests that it may be possible to develop better OSL materials for proton dosimetry if the dose response can be controlled during synthesis. Nevertheless, the degree in which the response to proton beams can be controlled remains to be determined. The research is funded by the Oklahoma Center for the Advancement of Science and Technology (OCAST), project number HR12-055.« less

Doping Y 2O 3 with Mn 4+ for energy-efficient lighting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ming, Wenmei; Shi, Hongliang; Du, Mao-Hua

Developing energy-efficient LEDs that emit warm white light requires new red phosphors with appropriate emission wavelengths and band widths. Mn 4+-activated Y 2O 3 is a potential red LED phosphor with narrow emission and improved emission wavelength compared to previously known Mn 4+-activated oxide phosphors. Here in this work, the dopability and the oxidation state of Mn in Y 2O 3 are investigated based on the formation energies of native defects, Mn dopants, and divalent co-dopants (i.e., Ca, Sr, Cd, and Zn) calculated using hybrid density functional theory. We found that Mn 4+ is difficult to form in Y 2Omore » 3 without co-doping. Stabilizing Mn 4+ on Y 3+ sites (forming Mn + Y donors) requires the co-doping of compensating acceptors (Ca or Sr) in oxygen-rich growth environments.« less

Doping Y 2O 3 with Mn 4+ for energy-efficient lighting

DOE PAGES

Ming, Wenmei; Shi, Hongliang; Du, Mao-Hua

2018-03-28

Developing energy-efficient LEDs that emit warm white light requires new red phosphors with appropriate emission wavelengths and band widths. Mn 4+-activated Y 2O 3 is a potential red LED phosphor with narrow emission and improved emission wavelength compared to previously known Mn 4+-activated oxide phosphors. Here in this work, the dopability and the oxidation state of Mn in Y 2O 3 are investigated based on the formation energies of native defects, Mn dopants, and divalent co-dopants (i.e., Ca, Sr, Cd, and Zn) calculated using hybrid density functional theory. We found that Mn 4+ is difficult to form in Y 2Omore » 3 without co-doping. Stabilizing Mn 4+ on Y 3+ sites (forming Mn + Y donors) requires the co-doping of compensating acceptors (Ca or Sr) in oxygen-rich growth environments.« less

Influence of thermal history on the electrochemical properties of Li[Ni0.5Mn1.5]O4

NASA Astrophysics Data System (ADS)

Liu, Guoqiang; Park, Kyu-Sung; Song, Jie; Goodenough, John B.

2013-12-01

The oxygen-stoichiometric spinel Li[Ni0.5Mn1.5]O4 is an insulator with ordered Ni(II) and Mn(IV). Although it delivers 4.7 V versus Li, the ordered phase gives poor performance as the cathode of a Li-ion battery. Here we demonstrate control of the degree of cation order by adjusting the oxygen stoichiometry with thermal history of the synthesis rather than by doping 2M(III) for Ni(II) + Mn(IV) (M = Cr, Mn, Fe, Co, Al, Ga). We report retention of capacity near 100 mAh g-1 at room temperature at 10C/10C charge/discharge rate with little capacity fade; at 55 °C, a capacity fade occurs as a result of reaction with the electrolyte, but it is reduced to a level comparable to that obtained by doping.

Role of Cu-Ion Doping in Cu-α-MnO 2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction

DOE PAGES

Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.; ...

2014-07-09

The role of Cu-ion doping in α-MnO 2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO 2 nanowires (Cu-α-MnO 2) were prepared with varying amounts of Cu 2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO 2 nanowires have higher terminal current densities, enhanced kinetic rate constants, and improved charge transfer resistances that trend with Cu-content, exceeding values attained by α-MnO 2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn 3+ content for the Cu-α-MnO 2 nanowires. The Mn 3+/Mn 4+ couple is themediator for the rate-limiting redoxmore » driven O 2 -/OH - exchange. It is proposed that O 2 adsorbs viaan axial site (the e g orbital on the Mn 3+ d 4 ion) at the surface, or at edge defects, of the nanowireand that the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O 2 adsorbates and faster rates of reduction. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the ORR in alkaline electrolyte and an increase in Mn 3+ character of the oxide.« less

Doping effects on the relaxation of frustration and magnetic properties of YMn0.9Cu0.1O3

NASA Astrophysics Data System (ADS)

Xiao, L. X.; Xia, Z. C.; Wang, X.; Ni, Y.; Yu, W.; Shi, L. R.; Jin, Z.; Xiao, G. L.

2017-12-01

The crystal structure and magnetic properties of hexagonal YMn0.9Cu0.1O3 single crystal are systematically investigated. The refinement results of XRD show the lattice constant decreases, which is unusually due to the doped Cu2+ ion has a larger ionic radius than the Mn3+ ions. The XPS results show that the coexistence of Mn2+, Mn3+ and Mn4+ ions in YMn0.9Cu0.1O3 single crystal. Magnetization measurements show that Cu doped YMn0.9Cu0.1O3 and parent YMnO3 have almost the same antiferromagnetic transition temperature TN, which indicates the AFM interaction is robust in the geometry frustrated system. Because doping directly destroy some of the Mn3+ ions nets, the relaxation of frustration of Mn in-plane 2D triangular geometry network leads to the significantly decrease of Mn3+ ions AFM interaction. In addition, the coexistence and competition between the ferromagnetic and antiferromagnetic interactions among the Mn2+, Mn3+ and Mn4+ ions lead to a complicated and irreversible magnetization behavior in YMn0.9Cu0.1O3 single crystal.

Influences of Ru-doping on the magnetic properties of Ca0.85Pr0.15Mn1- x Ru x O3

NASA Astrophysics Data System (ADS)

Phan, T. L.; Zhang, Y. D.; Yu, S. C.; Thanh, P. Q.; Yen, P. D. H.

2012-11-01

CaMnO3 is an antiferromagnet, in which the super-exchange interaction taking place between Mn4+ ions plays an important role. The doping of a small amount of 15% Pr into the Ca site, Ca0.85Pr0.15MnO3, leads to the appearance of Mn3+ ions, and introduces the ferromagnetic (FM) double-exchange interaction between Mn3+ and Mn4+ ions, which is dominant in a narrow temperature range of 90 ˜ 115 K. The FM interaction becomes strong for Ca0.85Pr0.15MnO3 doped with 4 and 8% Ru into the Mn site ( i.e., Ca0.85Pr0.15Mn1- x Ru x O3 with x = 0.04 and 0.08). The Curie temperature obtained for x = 0.04 and 0.08 are about 135 and 180 K, respectively. While the FM interaction in the former is dominant due to Mn3+-Mn4+ exchange pairs, the latter has the contribution of Ru ions. This results in remarkable differences in the features of their FM-paramagnetic phase transitions and their coercive fields H c .

Synthesis and electrochemical characteristics of LiCr xNi 0.5- xMn 1.5O 4 spinel as 5 V cathode materials for lithium secondary batteries

NASA Astrophysics Data System (ADS)

Hong, Ki-Joo; Sun, Yang-Kook

A series of electrochemical spinel compounds, LiCr xNi 0.5- xMn 1.5O 4 ( x=0, 0.1, 0.3), are synthesized by a sol-gel method and their electrochemical properties are characterized in the voltage range of 3.5-5.2 V. Electrochemical data for LiCr xNi 0.5- xMn 1.5O 4 electrodes show two reversible plateaus at 4.9 and 4.7 V. The 4.9 V plateau is related to the oxidation of chromium while the 4.7 V plateau is ascribed to the oxidation of nickel. The LiCr 0.1Ni 0.4Mn 1.5O 4 electrode delivers a high initial capacity of 152 mAh g -1 with excellent cycleability. The excellent capacity retention of the LiCr 0.1Ni 0.4Mn 1.5O 4 electrode is largely attributed to structural stabilization which results from co-doping (chromium and nickel) and increased theoretical capacity due to substitution of chromium.

Effect of Mn doping on the temperature-dependent anomalous giant dielectric behavior of CaCu3Ti4O12

NASA Astrophysics Data System (ADS)

Kim, C. H.; Jang, Y. H.; Seo, S. J.; Song, C. H.; Son, J. Y.; Yang, Y. S.; Cho, J. H.

2012-06-01

We report dielectric properties and dielectric relaxation behaviors of Mn-substituted CaCu3Ti4O12 (CCTO) on Cu sites. While CCTO exhibits the giant dielectric constant and low dielectric loss in a wide temperature range, drastic suppression of the dielectric constant in Mn-doped CCTO (CCMTO) samples have been observed in temperature and frequency dependencies of dielectric properties with two possible origins as Mn doping increases. The observed suppression of dielectric response in the low Mn doping differs from the heavy doping of Mn in CCMTO samples. The low-Mn-doped CCMTO samples (x=0.01 and 0.02) show that the relaxation time and the activation energy Ea were slightly reduced due to a decreased contribution from the density of the dipolar effect. However, in heavily doped CCMTO samples (x=0.03, 0.04, and 0.05), the dielectric response, relaxation time, and Ea were significantly decreased, suggesting Mn doping plays a significant role in the destruction of the intrinsic dipolar effect.

Magnetic interactions in La0.7Sr0.3Mn1-xMexO3 (Me=Ga, Fe, Cr) manganites

NASA Astrophysics Data System (ADS)

Troyanchuk, I. O.; Bushinsky, M. V.; Karpinsky, D. V.; Tereshko, N. V.; Dobryansky, V. M.; Többens, D. M.; Sikolenko, V.; Efimov, V.

2015-11-01

Magnetic properties and crystal structure of La0.7Sr0.3Mn1-xMexO3 (Me=Ga, Fe, Cr; x≤0.3) have been studied by neutron powder diffraction and magnetization measurements. It is shown that substitution of manganese ions by chromium or gallium ions (x=0.3) leads to phase separation into antiferromagnetic and ferromagnetic phases whereas replacement by Fe ions stabilizes spin glass state (x=0.3). Ferromagnetic interactions in Cr-substituted compounds are much more pronounced than in Fe- and Ga-doped ones. Magnetic properties are discussed in the model assuming a dominance of superexchange interactions. It is considered that ferromagnetism in the Cr-substituted compositions is associated with nearly equal contributions from positive and negative components of the superexchange interaction between Mn3+ and Cr3+ ions as well as to mixed valence of chromium ions. The spin glass state observed for the Fe-doped sample (x=0.3) is associated with strong antiferromagnetic superexchange between Fe3+-O-Fe3+ and Fe3+-O-(Mn3+, Mn4+).

Spin reversal and ferroelectricity in perovskite Dy{sub 0.7}Sr{sub 0.3}MnO{sub 3} and Dy{sub 0.6}Sr{sub 0.4}MnO{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Y.; Cao, S. X.; Ren, W., E-mail: renwei@shu.edu.cn

2015-08-17

Multiferroic materials which simultaneously exhibit electric polarization and magnetism have attracted more and more attention due to their novel physical properties and promising applications. Here, we report the magnetic and ferroelectric properties of single phase perovskite manganites Dy{sub 0.7}Sr{sub 0.3}MnO{sub 3} and Dy{sub 0.6}Sr{sub 0.4}MnO{sub 3} by varying temperature and magnetic field. Our results reveal that there exist spin reversal and strong antiferromagnetic pinning effects in both compounds, as well as negative magnetization in Dy{sub 0.6}Sr{sub 0.4}MnO{sub 3}. Moreover, upon Sr-doping, spontaneous electric polarizations have been observed and the maximum polarization value of Dy{sub 0.7}Sr{sub 0.3}MnO{sub 3} is about 1000 μC/m{supmore » 2} while Dy{sub 0.6}Sr{sub 0.4}MnO{sub 3} reaches to 2000 μC/m{sup 2}. The onset of the ferroelectric transition temperature is enhanced to be around 60 K. Our results indicate that the antiferromagnetic coupling is relevant to the ferroelectric properties of these fascinating multiferroic systems.« less

Effects of Nb doping level on the electronic transport, photoelectric effect and magnetoresistance across La0.5Ca0.5MnO3/Nb:SrTiO3 junctions

NASA Astrophysics Data System (ADS)

Wang, J. F.; Jiang, Y. C.; Chen, M. G.; Gao, J.

2013-12-01

Heterojunctions composed of La0.5Ca0.5MnO3 and Nb doped SrTiO3 were fabricated, and the effects of the Nb doping level on their electronic transport, photoelectric effect, and magnetoresistance were investigated. A lower doping concentration of Nb led to better rectifying properties and higher open circuit voltages. The I-V curves for La0.5Ca0.5MnO3/0.7 wt. % Nb-SrTiO3 showed a negligible response to magnetic fields for all temperatures, whereas La0.5Ca0.5MnO3/0.05 wt. % Nb-SrTiO3 exhibited distinct magnetoresistance, which depended on both the bias voltage and temperature. These results are discussed with the assistance of conventional semiconductor theories.

An innovative technique to synthesize C-doped MgB2 by using chitosan as the carbon source

NASA Astrophysics Data System (ADS)

Bovone, G.; Vignolo, M.; Bernini, C.; Kawale, S.; Siri, A. S.

2014-02-01

Here, we report a new technique to synthesize carbon-doped MgB2 powder. Chitosan was innovatively used as the carbon source during the synthesis of boron from boron oxide. This allowed the introduction of local defects, which later on served as pinning centers in MgB2, in the boron lattice itself, avoiding the traditional and time consuming ways of ex situ MgB2 doping (e.g. ball milling). Two volume percentages of C-doping have been tried and its effect on the superconducting properties, evaluated by magnetic and transport measurements, are discussed here. Morphological analysis by scanning electron microscopy revealed nano-metric grains’ distribution in the boron and MgB2 powder. Mono-filamentary MgB2 wires have been fabricated by an ex situ powder-in-tube technique by using the thus prepared carbon-doped MgB2 and pure MgB2 powders. Transport property measurements on these wires were made and compared with MgB2 wire produced using commercial boron.

Relation Between Crystal Structure and Electrochemical Performance of LiNi1/3Zn x Co1/3-xMn1/3O₂ (0.000 ≤ x ≤ 0.133).

PubMed

Wang, Xujun; Wan, Yong; Wang, Ruiqi; Xu, Xiantang; Wang, He; Chang, Mingning; Yuan, Feng; Ge, Xiaohui; Shao, Weiquan; Xu, Sheng

2018-04-01

LiNi1/3ZnxCo1/3-xMn1/3O2 (0.000 ≤ x ≤ 0.133) hollow microspheres are synthesized using MnO2 hollow microspheres both as a self-template and Mn source. These hollow microspheres, ~4 μm in diameter, are composed of approximately 300 nm basic nanoparticles. The XRD patterns of LiNi1/3ZnxCo1/3-xMn1/3O2 were analyzed by the RIETAN-FP program, and the obtained samples have a layered α-NaFeO2 structure. Electrochemical performances of the samples were carried out between 2.5 V and 4.5 V. The behavior of the lattice parameters is consistent with Cycling performance and rate performance change with increase of x. Compared with the others, the sample of x = 0.133 exhibits a relatively superior electrochemical performance. The specific capacity of x = 0.133 was increased by 10.7% than no-doped. In addition, the cyclic voltammograms curves of the second cycle show no significant alteration compared with the first cycle and the electrochemical impedance of zinc doping sample showed smaller transfer resistance than the no-doping sample.

Development and characterization of Mn{sup 2+}-doped MgO nanoparticles by solution combustion synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basha, Md. Hussain; Gopal, N. O., E-mail: nogopal@yahoo.com; Rao, J. L.

2015-06-24

Mn doped MgO Nanoparticles have been prepared by Solution Combustion Synthesis. The synthesized sample is characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Electron Paramagnetic Resonance (EPR). The prepared MgO:Mn (1 mol%) nano crystals appear to be of simple cubic crystalline phase with lattice parameters a = 4.218(2) Å and cell volume = 74.98 (7) Å{sup 3}. SEM micrograph of powders show highly porous, many agglomerates with irregular morphology, large voids, cracks and pores. EPR spectrum of the sample at room temperature exhibit an isotropic sextet hyperfine pattern, centered at g=1.99, characteristic if Mn{sup 2+} ions with S=I=5/2.The observedmore » g value and the hyperfine value reveal the ionic bonding between Mn{sup 2+} and its surroundings.« less

Mn-doping-induced photocatalytic activity enhancement of ZnO nanorods prepared on glass substrates

NASA Astrophysics Data System (ADS)

Putri, Nur Ajrina; Fauzia, Vivi; Iwan, S.; Roza, Liszulfah; Umar, Akrajas Ali; Budi, Setia

2018-05-01

Mn-doped ZnO nanorods were synthesized on glass substrates via a two-steps process of ultrasonic spray pyrolysis and hydrothermal methods with four different concentrations Mn-doping (0, 1, 3, and 7 mol%). Introduction of Mn into ZnO is known could enhance the photocatalytic activity owing to the increase in the defect sites that effectively suppress the recombination of free electrons and holes. In this study, results show that Mn-doping has effectively modified the nucleations and crystal growth of ZnO, as evidenced by the increasing in the diameter, height, and the number of nanorods per unit area, besides slightly reduced the band gap and increased the oxygen vacancy concentrations in the ZnO lattice. This condition has successfully multiplied the photocatalytic performance of the ZnO nanorods in the degradation of methylene blue (MB) compared to the undoped-ZnO sample where in the typical process the MB can be degraded approximately 77% within only 35 min under a UV light irradiation.

Effect of Ti4+ doping on magnetic properties of charge ordered Bi0.3Ca0.7MnO3

NASA Astrophysics Data System (ADS)

Yadav, Kamlesh; Singh, M. P.; Razavi, F. S.; Varma, G. D.

2017-07-01

The effect of Ti doping in Bi0.3Ca0.7Mn1-x Ti x O3 (where x  =  0.0, 0.015, 0.03, 0.05, 0.08, 0.12 and 0.16) on structural, magnetic and transport properties have been studied. The charge-ordering temperature (T CO) decreases gradually with increasing Ti doping content, and finally disappears completely for x  =  0.12. The Neel temperature (T N) also decreases with increasing Ti doping content. A transition to a cluster glass like state is observed at T  ⩽  T N. The zero field cooled/field cooled (ZFC/FC) magnetization decreases at high temperature (T  >  200 K) with increasing Ti content, whereas an opposite trend is observed at low temperature (T  <  200 K). Small exchange bias effect is also observed for x  =  0.08 at 10 K. The resistivity increases with increasing Ti doping content. The disorder induced by Ti doping on the Mn site plays a key role in explaining the observed magnetic and electrical properties.

Magnetic properties of M0.3Fe2.7O4 (M = Fe, Zn and Mn) ferrites nanoparticles

NASA Astrophysics Data System (ADS)

Modaresi, Nahid; Afzalzadeh, Reza; Aslibeiki, Bagher; Kameli, Parviz

2018-06-01

In the present article a comparative study on the structural and magnetic properties of nano-sized M0.3Fe0.7Fe2O4 (M = Fe, Zn and Mn) ferrites have been reported. The X-ray diffraction (XRD) patterns show that the crystallite size depends on the cation distribution. The Rietveld refinement of XRD patterns using MAUD software determines the distribution of cations and unit cell dimensions. The magnetic measurements show that the maximum and minimum value of saturation magnetization is obtained for Zn and Mn doped samples, respectively. The peak temperature of AC magnetic susceptibility of Zn and Fe doped samples below 300 K shows the superparamagnetic behavior in these samples at room temperature. the AC susceptibility results confirm the presence of strong interactions between the nanoparticles which leads to a superspin glass state in the samples at low temperatures.

Optical spectroscopy of disordered Ca3Ga2Ge4O14 crystal doped with manganese

NASA Astrophysics Data System (ADS)

Burkov, Vladimir; Alyabyeva, Liudmila; Mill, Boris; Kotov, Viacheslav

2018-05-01

Circular dichroism, absorption and luminescence spectra of single crystalline manganese doped calcium gallogermanate Ca3Ga2Ge4O14:Mn were investigated in 300-850 nm wavelength region in wide temperature range 8-300 K. Careful analysis of experimental results revealed presence of electron transitions typical for sixfold coordinated trivalent manganese ions with d4 electron configuration. Thus, manganese ions doping the crystal matrix of CCG incorporate into lattice in 1a octahedral site-positions substituting Ga3+ ions. The results obtained were compared with investigation of isostructural to CGG manganese doped langasite crystals, La3Ga5SiO14:Mn where dopant is in octahedral Mn4+ state.

Determination of theoretical capacity of metal ion-doped LiMn 2O 4 as the positive electrode in Li-ion batteries

NASA Astrophysics Data System (ADS)

Todorov, Yanko M.; Hideshima, Yasufumi; Noguchi, Hideyuki; Yoshio, Masaki

The theoretical capacity and cation vacancy of metal ion (M)-doped LiMn 2- xM xO 4 spinel compounds serving as positive electrodes in a 4-V lithium ion batteries are calculated. The capacity depends strongly on the mole fraction of doped metal ion and vacancies. The theoretical capacity increases with increasing oxidation number of the doped metal ion in the 16d site of LiMn 2O 4 at the same doping fraction. The validity of the proposed equation for calculation of the capacity has been initially confirmed using a metal ion with well-known valence, such as the Al ion. The oxidation state of Co, Ni and Cr ions in the spinel structure is found to be trivalent, divalent and trivalent, respectively. Analysis shows that metal ion-doped spinel compounds with low vacancy content promote high capacity.

Influence of iridium doping in MgB2 superconducting wires

NASA Astrophysics Data System (ADS)

Grivel, J.-C.

2018-04-01

MgB2 wires with iridium doping were manufactured using the in-situ technique in a composite Cu-Nb sheath. Reaction was performed at 700 °C, 800 °C or 900 °C for 1 h in argon atmosphere. A maximum of about 1.5 at.% Ir replaces Mg in MgB2. The superconducting transition temperature is slightly lowered by Ir doping. The formation of IrMg3 and IrMg4 secondary phase particles is evidenced, especially for a nominal stoichiometry with 2.0 at.% Ir doping. The critical current density and accommodation field of the wires are strongly dependent on the Ir content and are generally weakened in the presence of Ir, although the effect is less pronounced at lower temperatures.

Dependence of the magnetic properties of the dilute magnetic semiconductor Zn1-xMnxO nanorods on their Mn doping levels

NASA Astrophysics Data System (ADS)

Thongjamroon, S.; Ding, J.; Herng, T. S.; Tang, I. M.; Thongmee, S.

2017-10-01

The effects of Mn doping on the ferromagnetic properties of the dilute magnetic semiconductor Zn1-xMnxO nanorods (NR's) having the nominal composit-ions x = 0, 0.01, 0.03, 0.04 and 0.05 grown by a low temperature hydrothermal method are studied. Energy dispersive X-ray (EDX) is used to determine the actual amounts of the elements in each NR's. X-ray diffraction, scanning electron microscopy, photoluminescence and vibrating sample magnetometer measurements are used to observe the effects of the Mn substitution on the properties of the doped ZnO and to relate the changes in the properties to changes in the defect content. It is observed that the saturation magnetization of the Mn ions in the wurtzite structure varies from 0.0210 μB/Mn2+ to 0.0234 μB/Mn2+ reaching a high of 0.0251 μB/Mn2+ as the Mn concentrations is varied from 0.9 to 7.36 atomic%. It is argued that the changes in the saturation magnetization are due to the competition between the direct Mn-Mn exchange interaction and the indirect Mn-O-Mn exchange interaction in the doped Mn ZnO NP's.

Optical properties of 3d transition-metal-doped MgAl2O4 spinels

NASA Astrophysics Data System (ADS)

Izumi, K.; Miyazaki, S.; Yoshida, S.; Mizokawa, T.; Hanamura, E.

2007-08-01

Strong emission bands in the visible region are observed in MgAl2O4 crystals doped with transition-metal ions under excitation at the band-to-band transitions. We report optical responses of Cr-, Co-, and Ni-doped MgAl2O4 and present optical models for M -doped MgAl2O4 ( M=Ti , V, Cr, Mn, Co, and Ni) to describe the charge-transfer transitions and the transitions between multiplet levels of 3d electrons, which are observed competitively or coexisting, depending on the number of 3d electrons. While the optical responses of Cr- and Ni-doped MgAl2O4 are dominated by the multiplet-multiplet transitions, those of Ti- and V-doped MgAl2O4 are governed by the charge-transfer transitions. The two kinds of transitions coexist in the Mn- and Co-doped MgAl2O4 . These behaviors are well understood based on the numerical results of unrestricted Hartree-Fock approximation.

Evaluation of the magnetocaloric response of nano-sized La0.7Ca0.3Mn1-xNixO3 manganites synthesized by auto-combustion method

NASA Astrophysics Data System (ADS)

Gómez, Adrián; Chavarriaga, Edgar; Supelano, Iván; Parra, Carlos Arturo; Morán, Oswaldo

2018-05-01

A systematic study of the dependence of the magnetization on the magnetic field around the ferromagnetic-paramagnetic phase transition temperature is carried out on La0.7Ca0.3Mn1-xNixO3 (x=0, 0.02, 0.07, and 1) samples synthesized by auto-combustion method. The successful substitution of Mn3+ ions by Ni2+ ions in the La0.7Ca0.3MnO3 lattice is corroborated by X-ray diffraction technique. Banerjees criteria, Arrott plots, and the scaling hypothesis are used to analyze the experimental data. It is verified that the Ni-doping increases the operating temperature range for magnetocaloric effect through tuning of the magnetic transition temperature. Probably, the replacement of Mn3+ by Ni2+ ions in the La0.7Ca0.3MnO3 lattice weakens the Mn3+-O-Mn4+ double exchange interaction, which leads to a decrease in the transition temperature and magnetic moment in the samples. The Arrott plots suggest that the phase transition from ferromagnetic to paramagnetic in the nano-sized manganite is of second order. The analysis of the magnetization results show that the maximum magnetic entropy changes observed for x=0, 0.02, 0.07, and 0.1 compositions are 0.85, 0.77, 0.63, and 0.59 J/kg K, under a magnetic field of 1.5 T. These values indicate that the magnetic entropy change achieved for La0.7Ca0.3Mn1-xNixO3 manganites synthesized by auto-combustion method is higher than those reported for other manganites with comparable Ni-doping levels but synthesized by standard solid state reaction. It is also observed that the addition of Ni2+ increases the value of the relative cooling power as compared to that of the parent compound. The highest value of this parameter (˜60 J/kg) is found for a Ni-doping level of 2 % around 230 K in a field of 1.5 T.

Structural, dielectric and impedance spectroscopy studies in Co doped La0.7Te0.3MnO3

NASA Astrophysics Data System (ADS)

Uthaman, Bhagya; Revathy, R.; Job, Rojerce Brown; Varma, Manoj Raama

2018-05-01

The effect of cobalt doping on the structural and dielectric properties of the electron-doped manganite La0.7Te0.3Mn1-xCoxO3 (x=0, 0.1, 0.3 and 0.5) has been investigated. Cobalt substitution induces a structural transition from rhombohedral structure (R-3 c space group) to orthorhombic structure (Pbnm space group). It is observed that, dielectric constant decreases with Co concentration which could be due to suppression of double exchange (DE) interaction between Mn2+ and Mn3+. Also, the effect of the grain and grain boundary density on the dielectric response is studied using Cole-Cole plots.

Nanoscale-SiC doping for enhancing Jc and Hc2 in superconducting MgB2

NASA Astrophysics Data System (ADS)

Dou, S. X.; Braccini, V.; Soltanian, S.; Klie, R.; Zhu, Y.; Li, S.; Wang, X. L.; Larbalestier, D.

2004-12-01

The effect of nanoscale-SiC doping of MgB2 was investigated in comparison with undoped, clean-limit, and Mg-vapor-exposed samples using transport and magnetic measurements. It was found that there are two distinguishable but related mechanisms that control the critical current-density-field Jc(H ) behavior: increase of upper critical field Hc2 and improvement of flux pinning. There is a clear correlation between the critical temperature Tc, the resistivity ρ, the residual resistivity ratio RRR =R(300K)/R(40K), the irreversibility field H*, and the alloying state in the samples. The Hc2 is about the same within the measured field range for both the Mg-vapor-treated and the SiC-doped samples. However, the Jc(H ) for the latter is higher than the former in a high-field regime by an order of magnitude. Mg vapor treatment induced intrinsic scattering and contributed to an increase in Hc2. SiC doping, on the other hand, introduced many nanoscale precipitates and disorder at B and Mg sites, provoking an increase of ρ(40K ) from 1μΩcm (RRR=15) for the clean-limit sample to 300μΩcm (RRR=1.75) for the SiC-doped sample, leading to significant enhancement of both Hc2 and H * with only a minor effect on Tc. Electron energy-loss spectroscope and transmission electron microscope analysis revealed impurity phases: Mg2Si, MgO, MgB4, BOx, SixByOz, and BC at a scale below 10nm and an extensive domain structure of 2-4-nm domains in the doped sample, which serve as strong pinning centers.

Quick and enhanced degradation of bisphenol A by activation of potassium peroxymonosulfate to SO4rad - with Mn-doped BiFeO3 nanoparticles as a heterogeneous Fenton-like catalyst

NASA Astrophysics Data System (ADS)

Soltani, Tayyebeh; Tayyebi, Ahmad; Lee, Byeong-Kyu

2018-05-01

Mn-doped BiFeO3 magnetic nanoparticles (BFO MNPs), namely BiFe1-xMnxO3 (x = 0.05 and 0.10), were successfully synthesized using a simple and novel sol-gel method and then applied as a highly efficient peroxymonosulfate (KHSO5, PMS) activation catalyst for the fast degradation of bisphenol A (BPA) from aqueous solution. The strong PMS activation ability of 10% Mn-doped BFO MNPs without any metal leaching due to the simultaneous effects of iron and manganese ions in the production of radical sulfate (SO4rad -), caused complete BPA degradation in 15 min, which was much faster than that using combinations with H2O2. TOC was reduced to 33%, 23% and 13% by PMS activated with BFO, 5 and 10% Mn doped BFO, respectively, which are 2.1, 2.6 and 3.15-fold lower than that same nanoparticles activated with H2O2. The photocatalytic mechanism of BPA with the simultaneous effects of iron and manganese ions in Mn-doped BFO was explored. The addition of KBrO3 and NaNO3 salts into Mn-doped BFO/PMS system reduced the complete BPA degradation time to 10 min, whereas Na2CO3 and NaCl salt addition retarded it, because salt addition can generate radical species that are either more or less active than SO4rad -.

Evolution of magnetic properties of CaMn1-x Nb x O3 with Nb-doping

NASA Astrophysics Data System (ADS)

Markovich, V.; Fita, I.; Wisniewski, A.; Puzniak, R.; Martin, C.; Mogilyansky, D.; Jung, G.; Gorodetsky, G.

2015-08-01

Magnetic and structural properties of Nb-doped CaMnO3 have been studied and the effect of doping with 0.02  ⩽  x  ⩽  0.1 has been investigated. Substitution of Nb5+ ion for the Mn4+ site of the parent matrix causes one-electron doping with the chemical formula \\text{CaMn}1-2x4+\\text{Mn}x3+\\text{Nb}x5+{{\\text{O}}3} , accompanied by a monotonous increase of the lattice parameters, unit-cell volume, average Mn-O bond distance and a decrease in Mn-O-Mn bond angle, with increasing x. Low temperature magnetic ground state of CaMn1-x Nb x O3 has been found to be dependent on niobium doping level. The ground magnetic state evolves from mostly antiferromagnetic, with a weak ferromagnetic component for x = 0.02-0.08, to charge ordered C-type antiferromagnetic state at x = 0.1. Spontaneous magnetization increases sharply with increasing doping level, approaches a maximal value of 4.1 emu g-1 at T = 10 K for x = 0.08, and then decreases rapidly to reach a very small value of 0.2 emu g-1 for x = 0.1. Anomalous negative magnetization behavior below the magnetic transition temperature has been observed for the compound with x = 0.04 in the field cooled magnetization and remanent dc magnetization measurements. Vertical and horizontal shifts of the hysteresis loop of the field cooled sample have been observed for CaMn0.9Nb0.1O3 as possible signatures of the exchange bias effect. The effect of hydrostatic pressure on dc magnetization for the sample with x  >  0.02 revealed a significant increase of the ferromagnetic phase volume under pressure, linked to progressive suppression of a negative magnetization in x = 0.04 sample.

Tunable dielectric response and electronic conductivity of potassium-ion-doped tunnel-structured manganese oxides

NASA Astrophysics Data System (ADS)

He, Gaihua; Duan, Yuping; Song, Lulu; Zhang, Xuefeng

2018-06-01

Potassium-ion-doped MnO2 has been successfully synthesized using the hydrothermal method, and the influence of the doped potassium ions on the electrical conductivity and permittivity is studied. X-ray powder diffraction, scanning electron microscopy, electron-probe micro-analysis, and a vector network analyzer are used to perform characterization. The densities of states of doped and undoped MnO2 tunnel structures are also discussed based on first-principles calculations. Results show that the conductivity and dielectric resonance of MnO2 can be elevated by means of K+ doping. The conductivity of K+-doped MnO2 prepared at different reaction times shows a decreasing trend and is generally 1 order of magnitude higher than that of pure MnO2. The electrical conductivity of K+-doped MnO2 (R3) shows the highest value of 3.33 × 10-2 S/cm at the reaction time of 24 h, while that of pure MnO2 is 8.50 × 10-4 S/cm. When treated with acid, the conductivity of samples remains basically stable along with the increase of treatment time. In addition, acid treatment plays a very significant role in controlling the amount of K+ ions in crystals. The K+ contents of acid-treated samples are 5 times lower than that of the untreated R1. The dielectric losses of the samples with different reaction times are enhanced markedly with frequency increment. The complex permittivity of pure MnO2 only exhibits a resonance at ˜12 GHz, while K+-doped MnO2 exhibits another resonance behavior at ˜9 GHz. The capacity of the dielectric property in the net structure is enhanced by the interfacial polarization, dielectric relaxation, multiple internal reflections, and multiple scattering benefiting.

Investigation into the dehydration of selenate doped Na2M(SO4)2·2H2O (M = Mn, Fe, Co and Ni): Stabilisation of the high Na content alluaudite phases Na3M1.5(SO4)3-1.5x(SeO4)1.5x (M = Mn, Co and Ni) through selenate incorporation

NASA Astrophysics Data System (ADS)

Driscoll, L. L.; Kendrick, E.; Knight, K. S.; Wright, A. J.; Slater, P. R.

2018-02-01

In this paper we report an investigation into the phases formed on dehydration of Na2M(SO4)2-x(SeO4)x·2H2O (0 ≤ x ≤ 1; M = Mn, Fe, Co and Ni). For the Fe series, all attempts to dehydrate the samples doped with selenate resulted in amorphous products, and it is suspected that a side redox reaction involving the Fe and selenate may be occurring leading to phase decomposition and hence the lack of a crystalline product on dehydration. For M = Mn, Co, Ni, the structure observed was shown to depend upon the transition metal cation and level of selenate doping. An alluaudite phase, Na3M1.5(SO4)3-1.5x(SeO4)1.5x, was observed for the selenate doped compositions, with this phase forming as a single phase for x ≥ 0.5 M = Co, and x = 1.0 M = Ni. For M = Mn, the alluaudite structure is obtained across the series, albeit with small impurities for lower selenate content samples. Although the alluaudite-type phases Na2+2y(Mn/Co)2-y(SO4)3 have recently been reported [1,2], doping with selenate appears to increase the maximum sodium content within the structure. Moreover, the selenate doped Ni based samples reported here are the first examples of a Ni sulfate/selenate containing system exhibiting the alluaudite structure.

Structural, optical, and magnetic studies of manganese-doped zinc oxide hierarchical microspheres by self-assembly of nanoparticles.

PubMed

Hao, Yao-Ming; Lou, Shi-Yun; Zhou, Shao-Min; Yuan, Rui-Jian; Zhu, Gong-Yu; Li, Ning

2012-02-02

In this study, a series of manganese [Mn]-doped zinc oxide [ZnO] hierarchical microspheres [HMSs] are prepared by hydrothermal method only using zinc acetate and manganese acetate as precursors and ethylene glycol as solvent. X-ray diffraction indicates that all of the as-obtained samples including the highest Mn (7 mol%) in the crystal lattice of ZnO have a pure phase (hexagonal wurtzite structure). A broad Raman spectrum from as-synthesized doping samples ranges from 500 to 600 cm-1, revealing the successful doping of paramagnetic Mn2+ ions in the host ZnO. Optical absorption analysis of the samples exhibits a blueshift in the absorption band edge with increasing dopant concentration, and corresponding photoluminescence spectra show that Mn doping suppresses both near-band edge UV emission and defect-related blue emission. In particular, magnetic measurements confirm robust room-temperature ferromagnetic behavior with a high Curie temperature exceeding 400 K, signifying that the as-formed Mn-doped ZnO HMSs will have immense potential in spintronic devices and spin-based electronic technologies.

Synthesis of Spherical Al-Doping LiMn2O4 via a High-Pressure Spray-Drying Method as Cathode Materials for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhang, Yannan; Zhang, Yingjie; Zhang, Mingyu; Xu, Mingli; Li, Xue; Yu, Xiaohua; Dong, Peng

2018-05-01

Uniform and spherical LiAl0.075Mn1.925O4 particles have been successfully synthesized by the high-pressure spray-drying method. The structures and electrochemical properties of the particles were characterized by various techniques. Benefiting from the sphere-like morphology and Al-doping, LiAl0.075Mn1.925O4 delivers a capacity retention of 81.6% after 1000 cycles at 2°C, while LiMn2O4 exhibits a capacity retention of only 32.2%. The rate capability and reversible cycling performance are also improved. Furthermore, this work significantly alleviates the dissolution of Mn in LiMn2O4 materials, and effectively improves the transfer rate of lithium ions at the electrode/electrolyte interface. The spherical LiAl0.075Mn1.925O4 prepared by a facile method shows great potential for practical application in low-cost and long-life lithium-ion batteries.

Effect of (Mn,Cr) co-doping on structural, electronic and magnetic properties of zinc oxide by first-principles studies

NASA Astrophysics Data System (ADS)

Aimouch, D. E.; Meskine, S.; Boukortt, A.; Zaoui, A.

2018-04-01

In this study, structural, electronic and magnetic properties of Mn doped (ZnO:Mn) and (Mn,Cr) co-doped zinc oxide (ZnO:(Mn,Cr)) have been calculated with the FP-LAPW method by using the LSDA and LSDA+U approximations. Going through three configurations of Mn,Cr co-doped ZnO corresponding to three different distances between manganese and chromium, we have analyzed that ZnO:(Mn,Cr) system is more stable in its preferred configuration2. The lattice constant of undoped ZnO that has been calculated in this study is in a good agreement with the experimental and theoretical values. It was found to be increased by doping with Mn or (Mn,Cr) impurities. The band structure calculations showed the metallic character of Mn doped and Mn,Cr co-doped ZnO. As results, by using LSDA+U (U = 6eV), we show the half-metallic character of ZnO:Mn and ZnO:Mn,Cr. We present the calculated exchange couplings d-d of Mn doped ZnO which is in a good agreement with the former FPLO calculation data and the magnetization step measurement of the experimental work. The magnetic coupling between neighboring Mn impurities in ZnO is found to be antiferromagnetic. In the case of (Mn,Cr) co-doped ZnO, the magnetic coupling between Mn and Cr impurities is found to be antiferromagnetic for configuration1 and 3, and ferromagnetic for configuration2. Thus, the ferromagnetic coupling is weak in ZnO:Mn. Chromium co-doping greatly enhance the ferromagnetism, especially when using configuration2. At last, we present the 2D and 3D spin-density distribution of ZnO:Mn and ZnO:(Mn,Cr) where the ferromagnetic state in ZnO:(Mn,Cr) comes from the strong p-d and d-d interactions between 2p-O, 3d-Mn and 3d-Cr electrons. The results of our calculations suggest that the co-doping ZnO(Mn, Cr) can be among DMS behavior for spintronic applications.

Structural and optical characterizations of Ca2Al2SiO7:Ce3+, Mn2+ nanoparticles produced via a hybrid route

NASA Astrophysics Data System (ADS)

Teixeira, V. C.; Montes, P. J. R.; Valerio, M. E. G.

2014-07-01

Pure, Ce3+ doped and Ce3+ and Mn2+ co-doped Ca2Al2SiO7 ceramic powders were prepared by two different methodologies which are the proteic sol-gel process and a new hybrid route combining the proteic sol-gel with solid state reaction processes. The second one is an eco-friendly method because it uses natural raw materials in replacement of the metal alkoxides used in the traditional sol-gel routes. X-ray diffraction showed that Ca2Al2SiO7 crystalline phase was obtained for both preparations. Differential thermal analysis indicated that the exothermic event around 850 °C, for sample produced by proteic sol-gel method, and around 927 °C, for ceramics prepared by hybrid synthesis, can be associated to crystallization of Ca2Al2SiO7. Transmission electron microscope indicates that regular and spherical nanoparticles were obtained with average sizes of about 12 nm. The Scherrer's method was used to determine the average crystallite sizes and it was shown that nanometric crystallites were obtained of about 74 nm for samples produced via hybrid route. For all the single phase samples, the crystallite sizes are about the same and that agrees with TEM results. Diffuse optical reflectance measurements were used to estimate the Ca2Al2SiO7 optical band gap and the obtained value is about 6 eV, photoluminescence (PL) spectra presented typical emissions of Ce3+ and Mn2+ ions. Upon excitation at 352 nm the emission spectra showed a broad band centered at 415 nm due to the Ce3+ 4f1 → 5d1 typical transition. This emission is resonant with Mn2+ excitation and it transfers energy to Mn ions generating a second broad emission band centered at 620 nm due to the Mn2+. The PL results were used to obtain, as a fist approach, the Ce3+ energy levels diagram and, using the Tanabe-Sugano diagrams, the transitions due to the Mn2+ were calculated. X-ray excited optical luminescence measurements showed the same emission spectra as the PL emission spectra. Luminescence lifetime decay constants were measured for Ce and Mn co-doped and for Ce doped samples and the results indicate Ca2Al2SiO7:Ce3+, Mn2+ showed quite fast responses with main time constants below 30 ns.

Bulk magnetic properties of La1-xCaxMnO3 (0⩽x⩽0.14) : Signatures of local ferromagnetic order

NASA Astrophysics Data System (ADS)

Terashita, Hirotoshi; Neumeier, J. J.

2005-04-01

We report the bulk magnetic properties of hole-doped La1-xCaxMnO3 (0⩽x⩽0.14) in the paramagnetic and antiferromagnetic regions; the Mn4+ concentration was determined with chemical analysis. Significant enhancement of the effective paramagnetic moment illustrates the existence of ferromagnetic clusters (polarons). The data reveal a distinct crossover in the paramagnetic region, signifying competition between ferromagnetic clusters and antiferromagnetic correlations associated with the low-temperature magnetically ordered state. The results suggest similarity in the magnetic properties at low temperatures between hole-doped LaMnO3 and electron-doped CaMnO3 .

In Situ Growth of MnO2 Nanosheets on N-Doped Carbon Nanotubes Derived from Polypyrrole Tubes for Supercapacitors.

PubMed

Ou, Xu; Li, Qi; Xu, Dan; Guo, Jiangna; Yan, Feng

2018-03-02

Nitrogen-doped porous carbon nanotubes@MnO 2 (N-CNTs@MnO 2 ) nanocomposites are prepared through the in situ growth of MnO 2 nanosheets on N-CNTs derived from polypyrrole nanotubes (PNTs). Benefiting from the synergistic effects between N-CNTs (high conductivity and N doping level) and MnO 2 nanosheets (high theoretical capacity), the as-prepared N-CNTs@MnO 2 -800 nanocomposites show a specific capacitance of 219 F g -1 at a current density of 1.0 A g -1 , which is higher than that of pure MnO 2 nanosheets (128 F g -1 ) and PNTs (42 F g -1 ) in 0.5 m Na 2 SO 4 solution. Meanwhile, the capacitance retention of 86.8 % (after 1000 cycles at 10 A g -1 ) indicates an excellent electrochemical performance of N-CNTs@MnO 2 prepared in this work. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement of Hc2 and Jc by carbon-based chemical doping

NASA Astrophysics Data System (ADS)

Yeoh, W. K.; Dou, S. X.

2007-06-01

In the past 5 years, various kinds of doping of MgB 2, including single elements (metal and non-metal), silicates, various carbon sources, and other compounds have been investigated and reported. Most nanoparticle doping leads to improvement of critical current density, Jc( H), and performance, but some types show a negative effect. In this paper, the effect of carbon doping on Jc and the upper critical field, Hc2, of MgB 2 is reviewed. Carbon substitution effects make two distinguishable contributions to the enhancement of Jc field performance: increase of Hc2 and improvement of flux pinning, both because carbon substitutes for boron in the MgB 2 lattice. Among all the carbon sources so far, nano-SiC has been confirmed to be the most effective dopant to enhance the Jc in magnetic fields and Hc2. An irreversibility field, Hirr, of 10 T has been achieved with nano-SiC doping at 20 K, exceeding Hirr of NbTi at 4.2 K. Besides that, Hc2 of carbon alloyed MgB 2 film has reached the value of 71 T. The significant enhancement in Jc( H) and Hc2 via carbon substitution has provided great potential for practical applications of MgB 2. The dual reaction model proposed by the authors’ group provides a comprehensive understanding of the mechanism of enhancement in Jc and Hc2 by chemical doping. Further improvement in self-field Jc performance while maintaining the already achieved in-field performance remains as a major challenge in the development of MgB 2.

Phosphorescence detection of manganese(VII) based on Mn-doped ZnS quantum dots

NASA Astrophysics Data System (ADS)

Deng, Pan; Lu, Li-Qiang; Cao, Wei-Cheng; Tian, Xi-Ke

2017-02-01

The phosphorescent L-cysteine modified manganese-doped zinc sulfide quantum dots (L-cys-MnZnS QDs) was developed for a highly sensitive detection of permanganate anions (MnO4-). L-cys-MnZnS QDs, which were easily synthesized in aqueous media using safe and low-cost materials, can emit intense phosphorescence even though the solution was not deoxygenated. However, the phosphorescence of L-cys-Mn-ZnS QDs was strongly quenched by MnO4- ascribed to the oxidation of L-cys and the increase of surface defects on L-cys-MnZnS QDs. Under the optimal conditions, L-cys-MnZnS QDs offer high selectivity over other anions for MnO4- determination, and good linear Stern-Volmer equation was obtained for MnO4- in the range of 0.5-100 μM with a detection limit down to 0.24 μM. The developed method was finally applied to the detection of MnO4- in water samples, and the spike-recoveries fell in the range of 95-106%.

Synthesis, structure and electrochemistry of LiMn 2- yCr y/2 Cu y/2 O 4 (0.0⩽ y⩽0.5) prepared by wet chemistry

NASA Astrophysics Data System (ADS)

Julien, C.; Ruth Mangani, I.; Selladurai, S.; Massot, M.

2002-08-01

The LiMn 2O 4 co-doped with copper and chromium forming LiMn 2- yCr y/2 Cu y/2 O 4 spinel phases have been synthesized by wet chemistry technique using an aqueous solution of metal acetates and dicarboxylic acid (succinic acid) as a complexing agent. The structural properties of the synthesized products have been investigated by X-ray powder diffraction, Raman scattering, and Fourier-transform infrared spectroscopy. To improve the rechargeable capacity of Li//LiMn 2- yCr y/2 Cu y/2 O 4 cells, the electrochemical features of LiMn 2- yCr y/2 Cu y/2 O 4 compounds have been evaluated as positive electrode materials. The structural properties of these oxides are very similar to LiMn 2O 4, their electrochemical performances show that the capacity is maintained 95% of the initial value at the 36th cycle for y=0.1, this being explained by the change of Mn 3+/Mn 4+ ratio in doped phases.

Synthesis, characterization and vibrational spectroscopic study of Co, Mg co-doped LiMnPO4

NASA Astrophysics Data System (ADS)

Sronsri, Chuchai; Noisong, Pittayagorn; Danvirutai, Chanaiporn

2016-01-01

The isostructural olivine-like LiM(II)PO4 compounds [M(II) = Mn, Mn0.9Co0.1, Mn0.8Co0.1Mg0.1] were successfully generated through the solid state reaction from the synthesized NH4M(II)PO4• H2O precursors. The TG/DTG/DTA, AAS/AES, FTIR and XRD methods were employed to confirm both NH4M(II)PO4• H2O and LiM(II)PO4 compounds. Their morphologies were studied by SEM method. The shift of two theta angle of XRD to higher values was observed in metal doping compounds, which indicate the formation of the single phase of isodivalent doping of Co2 + and Mg2 + ions according to the change in the lattice parameters and cell volumes. Their infrared spectra are reported and discussed with respect to the normal vibrations of NH4+, PO43 -, P2O74 - and H2O molecules using factor group analysis. The correlation field splitting analysis of PO43 - in NH4M(II)PO4• H2O (orthorhombic system, Pmn21, C2v7 and Z = 2, [(3 × 5) - 6] × 2 = 18 internal modes) symbolized as Td - Cs - C2v7 suggested the number of vibrational modes to be: ΓVib = A1(6) + A2(3) + B1(6) + B2(3) and A1(6) + A2(3) + B1(3) + B2(6) for zx and yz plane respectively. While, LiM(II)PO4 crystallizes in the orthorhombic system the space group Pnma (D2h16), Z = 4 and the site symmetry of PO43 - is Cs. The correlation field splitting of type Td - Cs - D2h16 were reported in relation to [(3 × 5) - 6] × 4 = 36 internal modes for PO43 - unit in the structure.

Hierarchically porous MnO2 microspheres doped with homogeneously distributed Fe3O4 nanoparticles for supercapacitors.

PubMed

Zhu, Jian; Tang, Shaochun; Xie, Hao; Dai, Yuming; Meng, Xiangkang

2014-10-22

Hierarchically porous yet densely packed MnO2 microspheres doped with Fe3O4 nanoparticles are synthesized via a one-step and low-cost ultrasound assisted method. The scalable synthesis is based on Fe(2+) and ultrasound assisted nucleation and growth at a constant temperature in a range of 25-70 °C. Single-crystalline Fe3O4 particles of 3-5 nm in diameter are homogeneously distributed throughout the spheres and none are on the surface. A systematic optimization of reaction parameters results in isolated, porous, and uniform Fe3O4-MnO2 composite spheres. The spheres' average diameter is dependent on the temperature, and thus is controllable in a range of 0.7-1.28 μm. The involved growth mechanism is discussed. The specific capacitance is optimized at an Fe/Mn atomic ratio of r = 0.075 to be 448 F/g at a scan rate of 5 mV/s, which is nearly 1.5 times that of the extremely high reported value for MnO2 nanostructures (309 F/g). Especially, such a structure allows significantly improved stability at high charging rates. The composite has a capacitance of 367.4 F/g at a high scan rate of 100 mV/s, which is 82% of that at 5 mV/s. Also, it has an excellent cycling performance with a capacitance retention of 76% after 5000 charge/discharge cycles at 5 A/g.

The excellent performance of nest-like oxygen-deficient Cu1.5Mn1.5O4 applied in activated carbon air-cathode microbial fuel cell.

PubMed

Wang, Junjie; Tian, Pei; Li, Kexun; Ge, Baochao; Liu, Di; Liu, Yi; Yang, Tingting; Ren, Rong

2016-12-01

This study investigated the performance of nano spinel nest-like oxygen-deficient Cu 1.5 Mn 1.5 O 4 doping activated carbon (AC) as air cathode in microbial fuel cell (MFC). The Cu 1.5 Mn 1.5 O 4 was synthesized via hydrothermal method and subsequent annealed. The maximum power density (MPD) of MFC with oxygen-deficient Cu 1.5 Mn 1.5 O 4 modified cathode was 1928±18mWm -2 , which was 1.53 times higher than the bare cathode. The electrochemical studies showed that Cu 1.5 Mn 1.5 O 4 doping AC exhibited higher kinetic activity and lower resistance. The mechanism of oxygen reduction for the catalyst was a four electron pathway. The oxygen deficient of Cu 1.5 Mn 1.5 O 4 played an important role in catalytic activity. So Cu 1.5 Mn 1.5 O 4 would be an excellent promising catalyst for ORR in MFC. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ce3+ doping into 0.6Li2MnO3·0.4LiNi0.5Co0.2Mn0.3O2 as cathode material for Li-ion batteries applied in new energy vehicle

NASA Astrophysics Data System (ADS)

Peng, Han; Yao, Linxiao; Zhang, Ming

2018-06-01

The pristine Li1.20[Mn0.52Ni0.20Co0.08]O2 and Ce3+-doped Li1.20[Mn0.50Ni0.20Co0.08Ce0.02]O2 cathode materials have been synthesized by using the typical sol-gel method. The XRD, SEM, ICP-OES and galvanostatic charge-discharge tests were carried out to study the influence of Ce3+ doping on the crystal structural, morphology and electrochemical properties of Li1.20Mn0.54Ni0.13Co0.13O2. The XRD result revealed the Ce3+ doping modification could decrease the cation mixing degree. The galvanostatic charge-discharge tests results showed that the sample after Ce3+ doping demonstrated the smaller irreversible capacity loss, more stable cyclic performance and better rate capacity than those of the pristine one.

Synthesis, characterization, vibrational spectroscopy, and factor group analysis of partially metal-doped phosphate materials.

PubMed

Sronsri, Chuchai; Boonchom, Banjong

2018-04-05

A simple precipitating method was used to synthesize effectively a partially metal-doped phosphate hydrate (Mn 0.9 Mg 0.1 HPO 4 ·3H 2 O), whereas the thermal decomposition process of the above hydrate precursor was used to obtain Mn 1.8 Mg 0.2 P 2 O 7 and LiMn 0.9 Mg 0.1 PO 4 compounds under different conditions. To separate the overlapping thermal decomposition peak, a deconvolution technique was used, and the separated peak was applied to calculate the water content. The factor group splitting analysis was used to exemplify their vibrational spectra obtained from normal vibrations of HPO 4 2- , H 2 O, P 2 O 7 4- and PO 4 3- functional groups. Further, the deconvoluted bending mode of water was clearly observed. Mn 0.9 Mg 0.1 HPO 4 ·3H 2 O was observed in the orthorhombic crystal system with the space group of Pbca (D 2h 15 ). The formula units per unit cell were found to be eight (Z = 8), and the site symmetric type of HPO 4 2- was observed as C s . For the HPO 4 2- unit, the correlation filed splitting analysis of type C 3v  - C s  - D 2h 15 was calculated and had 96 internal modes, whereas H 2 O in the above hydrate was symbolized as C 2v  - C s  - D 2h 15 and had 24 modes. The symbol C 2v  - C s  - C 2h 3 was used for the correlation filed splitting analysis of P 2 O 7 4- in Mn 1.8 Mg 0.2 P 2 O 7 (monoclinic, C2/m (C 2h 3 ), Z = 2, and 42 modes). Finally, the symbol T d  - C s  - D 2h 16 was used for the correlation filed splitting analysis of PO 4 3- in LiMn 0.9 Mg 0.1 PO 4 (orthorhombic, Pnma (D 2h 16 ), Z = 4, and 36 modes). Copyright © 2018 Elsevier B.V. All rights reserved.

Toxicological aspects of photocatalytic degradation of selected xenobiotics with nano-sized Mn-doped TiO2.

PubMed

Ozmen, Murat; Güngördü, Abbas; Erdemoglu, Sema; Ozmen, Nesrin; Asilturk, Meltem

2015-08-01

The toxic effects of two selected xenobiotics, bisphenol A (BPA) and atrazine (ATZ), were evaluated after photocatalytic degradation using nano-sized, Mn-doped TiO2. Undoped and Mn-doped TiO2 nanoparticles were synthesized. The samples were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), UV-vis-diffuse reflectance spectra (DRS), X-ray fluorescence spectroscopy (XRF), and BET surface area. The photocatalytic efficiency of the undoped and Mn-doped TiO2 was evaluated for BPA and ATZ. The toxicity of the synthesized photocatalysts and photocatalytic by-products of BPA and ATZ was determined using frog embryos and tadpoles, zebrafish embryos, and bioluminescent bacteria. Possible toxic effects were also evaluated using selected enzyme biomarkers. The results showed that Mn-doped TiO2 nanoparticles did not cause significant lethality in Xenopus laevis embryos and tadpoles, but nonfiltered samples caused lethality in zebrafish. Furthermore, Mn-doping of TiO2 increased the photocatalytic degradation capability of nanoparticles, and it successfully degraded BPA and AZT, but degradation of AZT caused an increase of the lethal effects on both tadpoles and fish embryos. Degradation of BPA caused a significant reduction of lethal effects, especially after 2-4h of degradation. However, biochemical assays showed that both Mn-doped TiO2 and the degradation by-products caused a significant change of selected biomarkers on X. laevis tadpoles; thus, the ecological risks of Mn-doped TiO2 should be considered due to nanomaterial applications and for spilled nanoparticles in an aquatic ecosystem. Also, the risk of nanoparticles should be considered using indicator reference biochemical markers to verify the environmental health impacts. Copyright © 2015 Elsevier B.V. All rights reserved.

Combined optical/MCD/ODMR investigations of photochromism in doubly-doped Bi12GeO20

NASA Astrophysics Data System (ADS)

Briat, B.; Borowiec, M. T.; Rjeily, H. B.; Ramaz, F.; Hamri, A.; Szymczak, H.

Electron paramagnetic resonance is detected optically via the change of magnetic circular dichroism under microwaves at 35 GHz. The technique is applied to Bi12GeO20 samples co-doped with vanadium and a second transition metal (Cr, Mn, Co, Cu). The optical and magnetic properties of several paramagnetic defects (V-Ge(4+) and Cr-Ge(4+)) are directly correlated. The basic photochromic processes occuring in samples doped with V, Mn, and Mn+V are explained. The V-Ge(4+/5+) level is positioned roughly 2.2 eV above the valence band.

Study of optical properties of BaMn1-xCrxO3 (x=0.0, 0.1, 0.2, 0.3, 0.4, 0.5) manganites using microwave synthesis method

NASA Astrophysics Data System (ADS)

Rani, Reena; Yadav, Kamlesh

2015-08-01

Barium manganite (BaMnO3), a perovskite based material, has been studied extensively. BaMnO3 properties can be changed by doping different elements at manganese (Mn) lattice site. We have prepared BaMnO3 and BaMn1-xCrxO3 (x=0.1, 0.2, 0.3, 0.4, 0.5) by Microwave Synthesizer. Data obtained from Fourier Transform Infrared Spectroscopy (FTIR) that the band gap of pure BaMnO3 is less as compare to the Cr doped BaMnO3. It is also clear from the FTIR that the band gap decreased with increasing the concentration of chromium. Broaden peak at 3201 cm-1 correspond to the stretching vibration of hydroxyl group (OH or H2O). The peaks appear on 724, 863 and 974 cm-1 is corresponding to the stretching vibration of metal oxide (M-O) bonds in the BaMnO3. BaMnO3 have applications in memory storage devices.

Evaluation of pristine and Eu ₂O₃-added MgB ₂ ceramics for medical applications: hardness, corrosion resistance, cytotoxicity and antibacterial activity.

PubMed

Batalu, Dan; Stanciuc, Ana Maria; Moldovan, Lucia; Aldica, Gheorghe; Badica, Petre

2014-09-01

Nano- or micropowders of Eu2O3 were added to MgB2, resulting in a composition of (MgB2)0.975(EuO1.5)0.025. Pristine and doped samples were prepared using spark plasma sintering and tested for (i) Vickers hardness, (ii) pH evolution in phosphate-buffered saline solution, (iii) corrosion resistance (Tafel polarization curves), (iv) cytotoxicity (in vitro tests), and (v) antibacterial activity. Eu2O3 addition influenced the investigated properties. Solutions of MgB2-based samples show a relatively high saturation pH of 8.5. This value is lower than that of solutions incubated with Mg or other Mg-based biodegradable alloys reported in the literature. MgB2-based samples have lower electro-corrosion rates than Mg. Their Vickers hardness is 6.8-10.2GPa, and these values are higher than those of biodegradable Mg-based alloys. MgB2 has low in vitro biocompatibility, good antibacterial activity against Escherichia coli, and mild activity against Staphylococcus aureus. Our results suggest that MgB2-based materials deserve attention in biomedical applications, such as implants or sterile medical instruments. Copyright © 2014 Elsevier B.V. All rights reserved.

Combined effects Na and SO2 in flue gas on Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO by NH3 simulated by Na2SO4 doping

NASA Astrophysics Data System (ADS)

Zhou, Aiyi; Yu, Danqing; Yang, Liu; Sheng, Zhongyi

2016-08-01

A series of Mn-Ce/TiO2 catalysts were synthesized through an impregnation method and used for low temperature selective catalytic reduction (SCR) of NOx with ammonia (NH3). Na2SO4 was added into the catalyst to simulate the combined effects of alkali metal and SO2 in the flue gas. Experimental results showed that Na2SO4 had strong and fluctuant influence on the activity of Mn-Ce/TiO2, because the effect of Na2SO4 included pore occlusion and sulfation effect simultaneously. When Na2SO4 loading content increased from 0 to 1 wt.%, the SCR activities of Na2SO4-doped catalysts decreased greatly. With further increasing amount of Na2SO4, however, the catalytic activity increased gradually. XRD results showed that Na2SO4 doping could induce the crystallization of MnOx phases, which were also confirmed by TEM and SEM results. BET results showed that the surface areas decreased and a new bimodal mesoporous structure formed gradually with the increasing amount of Na2SO4. XPS results indicated that part of Ce4+ and Mn3+ were transferred to Ce3+ and Mn4+ due to the sulfation after Na2SO4 deposition on the surface of the catalysts. When the doped amounts of Na2SO4 increased, NH3-TPD results showed that the Lewis acid sites decreased and the Brønsted acid sites of Mn-Ce/TiO2 increased quickly, which could be considered as another reason for the observed changes in the catalytic activity. The decreased Mn and Ce atomic concentration, the changes of their oxidative states, and the variation in acidic properties on the surface of Na2SO4-doped catalysts could be the reasons for the fluctuant changes of the catalytic activity.

Effect of chemical pressure on the electronic phase transition in Ca 1-x Sr x Mn 7 O 12 films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huon, A.; Lee, D.; Herklotz, A.

Here, we demonstrate how chemical pressure affects the structural and electronic phase transitions of the quadruple perovskite CaMn 7O 12 by Sr doping, a compound that exhibits a charge-ordering transition above room temperature making it a candidate for oxide electronics. We also have synthesized Ca 1-xSr xMn 7O 12 (0 ≤ x ≤ 0.6) thin films by oxide molecular beam epitaxy on (LaAlO 3) 0.3(SrAl 0.5Ta 0.5O 3) 0.7 (LSAT) substrates. The substitution of Sr for Ca results in a linear expansion of the lattice, as revealed by X-ray diffraction. Temperature-dependent resistivity and X-ray diffraction measurements are used to demonstratemore » that the coupled charge-ordering and structural phase transitions can be tuned with Sr doping. An increase in Sr concentration acts to decrease the phase transition temperature (T*) from 426 K at x = 0 to 385 K at x = 0.6. Furthemore, the presence of a tunable electronic phase transition, above room temperature, points to the potential applicability of Ca 1-xSr xMn 7O 12 in sensors or oxide electronics, for example, via charge doping.« less

Effect of chemical pressure on the electronic phase transition in Ca 1-x Sr x Mn 7 O 12 films

DOE PAGES

Huon, A.; Lee, D.; Herklotz, A.; ...

2017-09-18

Here, we demonstrate how chemical pressure affects the structural and electronic phase transitions of the quadruple perovskite CaMn 7O 12 by Sr doping, a compound that exhibits a charge-ordering transition above room temperature making it a candidate for oxide electronics. We also have synthesized Ca 1-xSr xMn 7O 12 (0 ≤ x ≤ 0.6) thin films by oxide molecular beam epitaxy on (LaAlO 3) 0.3(SrAl 0.5Ta 0.5O 3) 0.7 (LSAT) substrates. The substitution of Sr for Ca results in a linear expansion of the lattice, as revealed by X-ray diffraction. Temperature-dependent resistivity and X-ray diffraction measurements are used to demonstratemore » that the coupled charge-ordering and structural phase transitions can be tuned with Sr doping. An increase in Sr concentration acts to decrease the phase transition temperature (T*) from 426 K at x = 0 to 385 K at x = 0.6. Furthemore, the presence of a tunable electronic phase transition, above room temperature, points to the potential applicability of Ca 1-xSr xMn 7O 12 in sensors or oxide electronics, for example, via charge doping.« less

Synthesis, characterization, vibrational spectroscopy, and factor group analysis of partially metal-doped phosphate materials

NASA Astrophysics Data System (ADS)

Sronsri, Chuchai; Boonchom, Banjong

2018-04-01

A simple precipitating method was used to synthesize effectively a partially metal-doped phosphate hydrate (Mn0.9Mg0.1HPO4·3H2O), whereas the thermal decomposition process of the above hydrate precursor was used to obtain Mn1.8Mg0.2P2O7 and LiMn0.9Mg0.1PO4 compounds under different conditions. To separate the overlapping thermal decomposition peak, a deconvolution technique was used, and the separated peak was applied to calculate the water content. The factor group splitting analysis was used to exemplify their vibrational spectra obtained from normal vibrations of HPO42-, H2O, P2O74- and PO43- functional groups. Further, the deconvoluted bending mode of water was clearly observed. Mn0.9Mg0.1HPO4·3H2O was observed in the orthorhombic crystal system with the space group of Pbca (D2h15). The formula units per unit cell were found to be eight (Z = 8), and the site symmetric type of HPO42- was observed as Cs. For the HPO42- unit, the correlation filed splitting analysis of type C3v - Cs - D2h15 was calculated and had 96 internal modes, whereas H2O in the above hydrate was symbolized as C2v - Cs - D2h15 and had 24 modes. The symbol C2v - Cs - C2h3 was used for the correlation filed splitting analysis of P2O74- in Mn1.8Mg0.2P2O7 (monoclinic, C2/m (C2h3), Z = 2, and 42 modes). Finally, the symbol Td - Cs - D2h16 was used for the correlation filed splitting analysis of PO43- in LiMn0.9Mg0.1PO4 (orthorhombic, Pnma (D2h16), Z = 4, and 36 modes).

Structure, morphology and optical properties of undoped and MN-doped ZnO(1-x)Sx nano-powders prepared by precipitation method

NASA Astrophysics Data System (ADS)

Dejene, F. B.; Onani, M. O.; Koao, L. F.; Wako, A. H.; Motloung, S. V.; Yihunie, M. T.

2016-01-01

The undoped and Mn-doped ZnO(1-x)Sx nano-powders were successfully synthesized by precipitation method without using any capping agent. Its structure, morphology, elemental analysis, optical and luminescence properties were determined by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), UV-vis spectroscopy (UV) and photoluminescence spectroscopy (PL). A typical SEM image of the un-doped ZnO(1-x)Sx nanoparticles exhibit flake like structures that changes to nearly spherical particles with Mn-doping. The XRD of undoped and Mn doped ZnO(1-x)Sx pattern reveals the formation of a product indexed to the hexagonal wurtzite phase of ZnS. The nanopowders have crystallite sizes estimated from XRD measurements were in the range of 10-20 nm. All the samples showed absorption maximum of ZnO(1-x)Sx at 271 nm and high transmittance in UV and visible region, respectively. The undoped ZnO(1-x)Sx nanoparticles show strong room-temperature photoluminescence with four emission bands centering at 338 nm, 384 nm, 448 nm and 705 nm that may originate to the impurity of ZnO(1-x)Sx, existence of oxide related defects. The calculated bandgap of the nanocrystalline ZnO(1-x)Sx showed a blue-shift with respect to the Mn-doping. The PL spectra of the Mn-doped samples exhibit a strong orange emission at around 594 nm attributed to the 4T1-6A1 transition of the Mn2+ ions.

The Introduction of substitutional and non-substitutional dopants into MgB2 in high pressure/Temperature or non-equilibrium regimes

NASA Astrophysics Data System (ADS)

Sumption, Mike

2013-03-01

In an attempt to study the effect of doping of MgB2 under conditions leading to efficient doping, we used both an high temperature/high pressure induction furnace to dope into MgB2 bulks at temperatures up to 1600 C and 1500 Psi, and thin film, PLD multilayer and mixed layer film fabrication. The high temperature/high pressure formation was used to explore the solubility at high temperatures of various dopants, and the thin film formation was an attempt to use non-equilibrium conditions to inject dopants more effectively. The dopants used were C, Ti, and Zr. C was seen to reach a maximal level at 4 at% C site substituted into MgB2, as evidenced by EPMA and XRD results. Zr, of interest as a possible Mg site substitution in MgB2 was not seen to enter into the MgB2 phase (instead segregating) in the bulk high temperature/high pressure experiments, but was seen to enter in during PLD, as evidenced by STEM and XRD results. Ti additions were attempted in the high pressures and temperature rig, with some evidence for dopant introduction. Critical field measurements on the Zr doped samples where seen to suppress Bc2 for all except very low levels of Ti addition, presumably associated with the much greater doping efficiency. This work was supported by the U.S. Department of Energy, High Energy Physics university Grant No. DE-FG02-95ER40900

MnTiO3-driven low-temperature oxidative coupling of methane over TiO2-doped Mn2O3-Na2WO4/SiO2 catalyst

PubMed Central

Wang, Pengwei; Zhao, Guofeng; Wang, Yu; Lu, Yong

2017-01-01

Oxidative coupling of methane (OCM) is a promising method for the direct conversion of methane to ethene and ethane (C2 products). Among the catalysts reported previously, Mn2O3-Na2WO4/SiO2 showed the highest conversion and selectivity, but only at 800° to 900°C, which represents a substantial challenge for commercialization. We report a TiO2-doped Mn2O3-Na2WO4/SiO2 catalyst by using Ti-MWW zeolite as TiO2 dopant as well as SiO2 support, enabling OCM with 26% conversion and 76% C2-C3 selectivity at 720°C because of MnTiO3 formation. MnTiO3 triggers the low-temperature Mn2+↔Mn3+ cycle for O2 activation while working synergistically with Na2WO4 to selectively convert methane to C2-C3. We also prepared a practical Mn2O3-TiO2-Na2WO4/SiO2 catalyst in a ball mill. This catalyst can be transformed in situ into MnTiO3-Na2WO4/SiO2, yielding 22% conversion and 62% selectivity at 650°C. Our results will stimulate attempts to understand more fully the chemistry of MnTiO3-governed low-temperature activity, which might lead to commercial exploitation of a low-temperature OCM process. PMID:28630917

Luminescence properties of Sr2Mg3P4O15:Mn2+ phosphor and the improvement by co-doping Bi3+

NASA Astrophysics Data System (ADS)

Cao, Renping; Wang, Wudi; Zhang, Jinlong; Ye, Yujiao; Chen, Ting; Guo, Siling; Xiao, Fen; Luo, Zhiyang

2018-05-01

Sr2Mg3P4O15:R (R = Bi3+, Mn2+, and Bi3+/Mn2+) phosphors are synthesized by a solid-state reaction method in air. Sr2Mg3P4O15:Bi3+ phosphor with excitation 380 nm shows blue light and its emission band peaking at ∼445 nm is observed. Under excitation at 355 and 416 nm, Sr2Mg3P4O15:Mn2+ phosphor shows red emission with a single broad emission band peaking at ∼630 nm in the range of 500-800 nm owing to the 4T1(G) → 6A1 transition of the Mn2+ ion. The optimal Mn2+ ion content in Sr2Mg3P4O15:Mn2+ phosphor is ∼0.05 and the lifetime of Sr2Mg2.95P4O15:0.05Mn2+ phosphor is ∼6.17 ms. After Bi3+ ion is co-doped, emission intensity of Sr2Mg3P4O15:Mn2+ phosphor can be enhanced obviously due to energy transfer (ET) from Bi3+ to Mn2+, which is confirmed by the luminescence properties and lifetimes of Sr2Mg3-xP4O15:Bi3+, Mn2+ phosphor. Luminous mechanism and ET process of Sr2Mg3-xP4O15:Bi3+, Mn2+ phosphor are explained by the simple energy level diagram of Bi3+ and Mn2+ ions.

Influences of annealing temperature on structural characterization and magnetic properties of Mn-doped BaTiO3 ceramics

NASA Astrophysics Data System (ADS)

Phan, The-Long; Zhang, P.; Grinting, D.; Yu, S. C.; Nghia, N. X.; Dang, N. V.; Lam, V. D.

2012-07-01

Polycrystalline samples of BaTiO3 doped with 2.0 at. % Mn were prepared by solid-state reaction at various temperatures (Tan) ranging from 500 to 1350 °C, used high-pure powders of BaCO3, TiO2, and MnCO3 as precursors. Experimental results obtained from x-ray diffraction patterns and Raman scattering spectra reveal that tetragonal Mn-doped BaTiO3 starts constituting as Tan ≈ 500 °C. The Tan increase leads to the development of this phase. Interestingly, there is the tetragonal-hexagonal transformation in the crystal structure of BaTiO3 as Tan ≈ 1100 °C. Such the variations influence directly magnetic properties of the samples. Besides paramagnetic contributions of Mn2+ centers traced to electron spin resonance, the room-temperature ferromagnetism found in the samples is assigned to exchange interactions taking place between Mn3+ and Mn4+ ions located in tetragonal BaTiO3 crystals.

Structural, dielectric and magnetic studies of Mn doped Y-type barium hexaferrite (Ba2Mg2Fe12O22)

NASA Astrophysics Data System (ADS)

Abdullah, Md. F.; Pal, P.; Mohapatra, S. R.; Yadav, C. S.; Kaushik, S. D.; Singh, A. K.

2018-04-01

The polycrystalline single phase Ba2Mg2Fe12O22 (BMF) and Ba2Mg2Fe11.52Mn0.48O22 (BMFM) were prepared using conventional solid state reaction route. We report the modification in structural, dielectric and magnetic properties of BMF due to 4% Mn doping at Fe site. Phase purity of both sample are confirmed by the Reitveld refinement of XRD data. Temperature dependent dielectric study shows decrease in dielectric constant (ɛ') and dielectric loss (tan δ) due to 4% Mn doping in parent sample. The ferrimagnetic to paramagnetic transition temperature (Tc) in doped sample decreases from 277°C to 150°C. Room temperature magnetization measurement shows ferrimagnetic behavior for both the samples. We have fitted the saturation magnetization data at 300 K by using least square method which confirms the enhancement of saturation magnetization and magnetic anisotropy constant in doped sample.

Chromium doping effects on structural and dielectric properties of Mn-Zn cobaltites

NASA Astrophysics Data System (ADS)

Yadav, A.; Dar, Mashkoor A.; Choudhary, P.; Shah, P.; Varshney, Dinesh

2016-05-01

The effect of transition metal Cr2+ ion as a dopant of Zn2+ in Mn0.5Zn0.5Co2O4 is investigated. Co-doped Mn0.5Zn0.5-xCrxCo2O4 (x = 0, 0.3 and 0.5) cobaltites were prepared by solid-state reaction route. X-ray powder diffraction (XRD) analysis reveals that the samples prepared are polycrystalline single-phase cubic spinel in structure having a space group Fd3m. An increase in average particle size observed with Cr2+ doping. However other structural parameters such as X-ray density, micro strain and dislocation density shows almost a similar decreasing trend with increase in Cr2+. High value of permittivity ˜105 is observed for the parent Mn0.5Zn0.5Co2O4 and shows a substantial decrease with increase in the Cr2+ doping. Higher doping of Cr2+ also increases the dielectric loss and hence limits its technological importance. At lower frequencies ac conductivity has been found to increase with increase in Cr2+ content.

Bulk oxides: asymmetry between p-and n-type transport properties

NASA Astrophysics Data System (ADS)

Maignan, Antioine

2015-03-01

The thermoelectric power (TEP) of transition metal oxides shows large difference depending on the sign of the charge carriers. In electron-doped oxides, the best TEs in terms of the figure of merit are heavily doped transparent conductors (as doped ZnO). The physics is very similar to that of semiconductors, though the defects chemistry differs: the existence of planar defects created by the doping elements, is far from the random distribution in semiconductors. In contrast the best p-types are layered cobaltites (CdI2 -type layers with edge-shared CoO6 octahedras). The Co cations adopt a low spin state. Both electronic correlations and spin entropy have to be considered to explain the S(T) curve for T <150K, whereas for T>150K, the spin/orbital configurations and the doping level in the generalized Heikes formula are dominating. This description supported by the results obtained for perovskite ruthenates was recently unvalidated for the quadruple perovskite ACu3Ru4O12, showing very different S(T) without S saturation up to ~ 900K. Their Pauli paramagnetism enlights the role of the spins upon thermopower. Similarly, searching for other n-types, interesting TE properties have been found in Ba1.2Mn8O16: the S(T) evidences a charge/orbital ordering in this manganite (vMn = 3.7) coupled to an abrupt change in the unit-cell volume. Ba1.2Mn8O16, although of n-type, exhibits a cst. | S | ~ 92 μV.K-1 for T>400K, explained by the generalized Heikes formula rather used for p-type. This difference with other n-type oxides is related to the Mn3+/Mn4+ magnetism and the contribution of eg orbitals for the transport properties. In this presentation, the richness of the TE properties of metal transition oxides will be emphasized focusing on the important role of the spins.

Charge storage mechanisms of manganese oxide nanosheets and N-doped reduced graphene oxide aerogel for high-performance asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Seubsai, Anusorn; Chanlek, Narong; Kidkhunthod, Pinit; Sangthong, Winyoo; Maensiri, Santi; Yimnirun, Rattikorn; Nilmoung, Sukanya; Pannopard, Panvika; Ittisanronnachai, Somlak; Kongpatpanich, Kanokwan; Limtrakul, Jumras; Sawangphruk, Montree

2016-11-01

Although manganese oxide- and graphene-based supercapacitors have been widely studied, their charge storage mechanisms are not yet fully investigated. In this work, we have studied the charge storage mechanisms of K-birnassite MnO2 nanosheets and N-doped reduced graphene oxide aerogel (N-rGOae) using an in situ X-ray absorption spectroscopy (XAS) and an electrochemical quart crystal microbalance (EQCM). The oxidation number of Mn at the MnO2 electrode is +3.01 at 0 V vs. SCE for the charging process and gets oxidized to +3.12 at +0.8 V vs. SCE and then reduced back to +3.01 at 0 V vs. SCE for the discharging process. The mass change of solvated ions, inserted to the layers of MnO2 during the charging process is 7.4 μg cm-2. Whilst, the mass change of the solvated ions at the N-rGOae electrode is 8.4 μg cm-2. An asymmetric supercapacitor of MnO2//N-rGOae (CR2016) provides a maximum specific capacitance of ca. 467 F g-1 at 1 A g-1, a maximum specific power of 39 kW kg-1 and a specific energy of 40 Wh kg-1 with a wide working potential of 1.6 V and 93.2% capacity retention after 7,500 cycles. The MnO2//N-rGOae supercapacitor may be practically used in high power and energy applications.

Charge storage mechanisms of manganese oxide nanosheets and N-doped reduced graphene oxide aerogel for high-performance asymmetric supercapacitors.

PubMed

Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Seubsai, Anusorn; Chanlek, Narong; Kidkhunthod, Pinit; Sangthong, Winyoo; Maensiri, Santi; Yimnirun, Rattikorn; Nilmoung, Sukanya; Pannopard, Panvika; Ittisanronnachai, Somlak; Kongpatpanich, Kanokwan; Limtrakul, Jumras; Sawangphruk, Montree

2016-11-18

Although manganese oxide- and graphene-based supercapacitors have been widely studied, their charge storage mechanisms are not yet fully investigated. In this work, we have studied the charge storage mechanisms of K-birnassite MnO 2 nanosheets and N-doped reduced graphene oxide aerogel (N-rGO ae ) using an in situ X-ray absorption spectroscopy (XAS) and an electrochemical quart crystal microbalance (EQCM). The oxidation number of Mn at the MnO 2 electrode is +3.01 at 0 V vs. SCE for the charging process and gets oxidized to +3.12 at +0.8 V vs. SCE and then reduced back to +3.01 at 0 V vs. SCE for the discharging process. The mass change of solvated ions, inserted to the layers of MnO 2 during the charging process is 7.4 μg cm -2 . Whilst, the mass change of the solvated ions at the N-rGO ae electrode is 8.4 μg cm -2 . An asymmetric supercapacitor of MnO 2 //N-rGO ae (CR2016) provides a maximum specific capacitance of ca. 467 F g -1 at 1 A g -1 , a maximum specific power of 39 kW kg -1 and a specific energy of 40 Wh kg -1 with a wide working potential of 1.6 V and 93.2% capacity retention after 7,500 cycles. The MnO 2 //N-rGO ae supercapacitor may be practically used in high power and energy applications.

Charge storage mechanisms of manganese oxide nanosheets and N-doped reduced graphene oxide aerogel for high-performance asymmetric supercapacitors

PubMed Central

Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Seubsai, Anusorn; Chanlek, Narong; Kidkhunthod, Pinit; Sangthong, Winyoo; Maensiri, Santi; Yimnirun, Rattikorn; Nilmoung, Sukanya; Pannopard, Panvika; Ittisanronnachai, Somlak; Kongpatpanich, Kanokwan; Limtrakul, Jumras; Sawangphruk, Montree

2016-01-01

Although manganese oxide- and graphene-based supercapacitors have been widely studied, their charge storage mechanisms are not yet fully investigated. In this work, we have studied the charge storage mechanisms of K-birnassite MnO2 nanosheets and N-doped reduced graphene oxide aerogel (N-rGOae) using an in situ X-ray absorption spectroscopy (XAS) and an electrochemical quart crystal microbalance (EQCM). The oxidation number of Mn at the MnO2 electrode is +3.01 at 0 V vs. SCE for the charging process and gets oxidized to +3.12 at +0.8 V vs. SCE and then reduced back to +3.01 at 0 V vs. SCE for the discharging process. The mass change of solvated ions, inserted to the layers of MnO2 during the charging process is 7.4 μg cm−2. Whilst, the mass change of the solvated ions at the N-rGOae electrode is 8.4 μg cm−2. An asymmetric supercapacitor of MnO2//N-rGOae (CR2016) provides a maximum specific capacitance of ca. 467 F g−1 at 1 A g−1, a maximum specific power of 39 kW kg−1 and a specific energy of 40 Wh kg−1 with a wide working potential of 1.6 V and 93.2% capacity retention after 7,500 cycles. The MnO2//N-rGOae supercapacitor may be practically used in high power and energy applications. PMID:27857225

Different Effects of Al Substitution for Mn or Fe on the Structure and Electrochemical Properties of Na0.67Mn0.5Fe0.5O2 as a Sodium Ion Battery Cathode Material.

PubMed

Wang, Huibo; Gao, Rui; Li, Zhengyao; Sun, Limei; Hu, Zhongbo; Liu, Xiangfeng

2018-05-07

P2-type layered oxides based on the elements Fe and Mn have attracted great interest as sodium ion battery (SIB) cathode materials owing to their inexpensive metal constituents and high specific capacity. However, they suffer from rapid capacity fading and complicated phase transformations. In this study, we modulate the crystal structure and optimize the electrochemical performances of Na 0.67 Mn 0.5 Fe 0.5 O 2 by Al doping for Mn or Fe, respectively, and the roles of Al in the enhancement of the rate capability and cycling performance are unraveled. (1) The substitution of Al for Mn or Fe decreases the lattice parameters a and c but enlarges d spacing and lengthens Na-O bonds, which enhances Na + diffusion and rate capability especially for Na 0.67 Mn 0.5 Fe 0.47 Al 0.03 O 2 . (2) Al doping reduces the thickness of TMO 2 and strengthens TM-O/O-O bonding. This enhances the layered structure stability and the capacity retention. (3) Al doping mitigates Mn 3+ and Jahn-Teller distortion, mitigating the irreversible phase transition. (4) Al doping also alleviates the lattice volume variation and the structure strain. This further improves the stability of the layered structure and the cycling performances particularly in the case of Al doping for Fe. The in-depth insights into the roles of Al substitution might be also useful for designing high-performance cathode materials for SIBs through appropriate lattice doping.

Superparamagnetic and ferrimagnetic behavior of nanocrystalline ZnO(MnO)

NASA Astrophysics Data System (ADS)

Kuryliszyn-Kudelska, I.; Dobrowolski, W.; Arciszewska, M.; Romčević, N.; Romčević, M.; Hadžić, B.; Sibera, D.; Narkiewicz, U.

2018-04-01

We have studied the magnetic properties of nanocrystals of ZnO:MnO prepared by traditional wet chemistry method. The detailed structural and morphological characterization was performed. The results of systematic measurements of AC magnetic susceptibility as a function of temperature and frequency as well as DC magnetization are reported. We observed two different types of magnetic behavior depending on the concentration doping. For samples with low nominal content (up to 30 wt% of MnO), superparamagnetic behavior was observed. We attribute the observed superparamagnetism to the presence of nanosized ZnMnO3 phase. For nanocrystals doped above nominal 60 wt% of MnO ferrimagnetism was detected with TC at around 42 K. This magnetic behavior we assign to the presence of nanosized Mn3O4 phase.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Yoejin; Park, Sangmoon, E-mail: spark@silla.ac.kr

Graphical abstract: - Highlights: • New near-ultraviolet (NUV)-excitable materials composed of Ba{sub 9}Eu{sub m}Mn{sub n}Y{sub 2}Si{sub 6}O{sub 24} (m = 0.01–0.5, n = 0–0.7) were prepared. • High energy-transfer from Eu{sup 2+} to Mn{sup 2+} and their energy-transfer mechanism were discussed. • The co-doping of Eu{sup 2+} and Mn{sup 2+} in the orthosilicate structure resulted in the emission of white light under NUV LED light. - Abstract: New single-phase and near-ultraviolet (NUV)-excitable materials composed of Ba{sub 9}Eu{sub m}Mn{sub n}Y{sub 2}Si{sub 6}O{sub 24} (m = 0.01–0.5, n = 0–0.7) were prepared via a solid-state reaction in reducing atmosphere. X-ray diffraction patternsmore » of the obtained phosphors were examined to index the peak positions. After doping the host structure with Eu{sup 2+} and Mn{sup 2+} emitters, the intense green, white, and orange emission lights that were observed in the photoluminescence spectra under NUV excitation were monitored. The dependence of the luminescent intensity of the Mn{sup 2+} co-doped (n = 0.1–0.7) host lattices on the fixed Eu{sup 2+} content (m = 0.1, 0.3, 0.5) is also investigated. Co-doping Mn{sup 2+} into the Eu{sup 2+}-doped host structure enabled a high energy-transfer from Eu{sup 2+} to Mn{sup 2+} and their energy-transfer mechanism were discussed. Using these phosphors, the desired CIE values including emissions throughout the green to orange regions of the spectra were achieved. Efficient white-light light-emitting diodes (LEDs) were fabricated using Eu{sup 2+} and Mn{sup 2+} co-doped phosphors based on NUV-excitable LED lights.« less

Structural transition in Mg-doped LiMn 2O 4: a comparison with other M-doped Li-Mn spinels

NASA Astrophysics Data System (ADS)

Capsoni, Doretta; Bini, Marcella; Chiodelli, Gaetano; Massarotti, Vincenzo; Mozzati, Maria Cristina; Azzoni, Carlo B.

2003-01-01

The charge distribution in the Mg-doped lithium manganese spinel Li 1.02Mg xMn 1.98- xO 4 with 0.00< x≤0.20 is discussed and compared to those pertinent to other M-doped samples (M=Ni 2+, Co 3+, Cr 3+, Al 3+ and Ga 3+). EPR spectra, low temperature X-ray diffraction and conductivity data are related to the cooperative Jahn-Teller (J-T) transition occurring at about 280 K in the undoped sample. The sensitivity of the cationic sublattice in displaying electronic and magnetic changes after substitution is remarked. The inhibition of the J-T transition is related to the ratio r=|Mn 4+|/|Mn 3+| as deduced from the charge distribution model [Li 1- xt+Mg xt2+] tetr[Li y+ xt+Mg xo2+Mn 1-3 y-2 x3+Mn 1+2 y+ x4+] octa where x= xo+ xt. For y=0.02 and x=0.02, a value r=1.177 is obtained, very close to rlim=1.18, the limit value beyond which the transition is inhibited.

Effect of Sr doping on the magnetic exchange interactions in manganites of type L a 1 - x S r x M n y A 1 - y O 3 ( A = Ga , Ti ; 0.1 ≤ y ≤ 1 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Furrer, Albert; Podlesnyak, Andrey A.; Pomjakushina, Ekaterina

Strontium doping transforms manganites of type La 1 - x Sr x Mn O 3 from an insulating antiferromagnet ( x = 0 ) to a metallic ferromagnet ( x > 0.16 ) due to the induced charge carriers (holes). We employed neutron scattering experiments in order to investigate the effect of Sr doping on a tailor-made compound of composition La 0.7 S r 0.3 M n 0.1 Ti 0.3 G a 0.6 O 3 . By the simultaneous doping with S r 2 + and Ti 4 + ions, the compound remains in the insulating state so thatmore » the magnetic interactions for large Sr doping can be studied in the absence of charge carriers. At T C = 215 K , there is a first-order reconstructive phase transition from the trigonal R - 3 c structure to the orthorhombic Pnma structure via an intermediate virtual configuration described by the common monoclinic subgroup P2 1 / c . The magnetic excitations associated with Mn 3 + dimers give evidence for two different nearest-neighbor ferromagnetic exchange interactions, in contrast to the undoped compound LaM n y A 1 - y O 3 where both ferromagnetic and antiferromagnetic interactions are present. Furthemore, the doping-induced changes of the exchange coupling originates from different Mn-O-Mn bond angles determined by neutron diffraction. The large fourth-nearest-neighbor interaction found for metallic manganites is absent in the insulating state. Here, we argue that the Ruderman-Kittel-Kasuya-Yosida interaction reasonably accounts for all the exchange couplings derived from the spin-wave dispersion in metallic manganites.« less

Effect of Sr doping on the magnetic exchange interactions in manganites of type L a 1 - x S r x M n y A 1 - y O 3 ( A = Ga , Ti ; 0.1 ≤ y ≤ 1 )

DOE PAGES

Furrer, Albert; Podlesnyak, Andrey A.; Pomjakushina, Ekaterina; ...

2017-03-14

Strontium doping transforms manganites of type La 1 - x Sr x Mn O 3 from an insulating antiferromagnet ( x = 0 ) to a metallic ferromagnet ( x > 0.16 ) due to the induced charge carriers (holes). We employed neutron scattering experiments in order to investigate the effect of Sr doping on a tailor-made compound of composition La 0.7 S r 0.3 M n 0.1 Ti 0.3 G a 0.6 O 3 . By the simultaneous doping with S r 2 + and Ti 4 + ions, the compound remains in the insulating state so thatmore » the magnetic interactions for large Sr doping can be studied in the absence of charge carriers. At T C = 215 K , there is a first-order reconstructive phase transition from the trigonal R - 3 c structure to the orthorhombic Pnma structure via an intermediate virtual configuration described by the common monoclinic subgroup P2 1 / c . The magnetic excitations associated with Mn 3 + dimers give evidence for two different nearest-neighbor ferromagnetic exchange interactions, in contrast to the undoped compound LaM n y A 1 - y O 3 where both ferromagnetic and antiferromagnetic interactions are present. Furthemore, the doping-induced changes of the exchange coupling originates from different Mn-O-Mn bond angles determined by neutron diffraction. The large fourth-nearest-neighbor interaction found for metallic manganites is absent in the insulating state. Here, we argue that the Ruderman-Kittel-Kasuya-Yosida interaction reasonably accounts for all the exchange couplings derived from the spin-wave dispersion in metallic manganites.« less

Manganese-induced magnetic symmetry breaking and its correlation with the metal-insulator transition in bilayered S r 3 ( R u 1 - x M n x ) 2 O 7

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qiang; Ye, Feng; Tian, Wei

Bilayered Sr 3Ru 2O 7 is an unusual metamagnetic metal with inherently antiferromagnetic (AFM) and ferromagnetic (FM) fluctuations. Partial substitution of Ru by Mn results in the establishment of a metal-insulator transition (MIT) at TMIT and AFM ordering at TM in Sr 3(Ru 1-xMn x) 2O 7. Using elastic neutron scattering, we investigated the effect of Mn doping on the magnetic structure, in-plane magnetic correlation lengths and their correlation to the MIT in Sr 3(Ru 1-xMn x) 2O 7 (x=0.06 and 0.12). With the increase of Mn doping (x) from 0.06 to 0.12 or the decrease of temperatures for x=0.12,more » an evolution from an in-plane short-range to long-range antiferromagnetic (AFM) ground state occurs. For both compounds, the magnetic ordering has a double-stripe configuration, and the onset of magnetic correlation with an anisotropic behavior coincides with the sharp rise in electrical resistivity and specific heat. Since it does not induce a measurable lattice distortion, the double-stripe antiferromagnetic order with anisotropic spin texture breaks symmetry from a C 4v crystal lattice to a C 2v magnetic sublattice. These observations shed light on an age-old question regarding the Slater versus Mott-type MIT.« less

Manganese-induced magnetic symmetry breaking and its correlation with the metal-insulator transition in bilayered S r 3 ( R u 1 - x M n x ) 2 O 7

DOE PAGES

Zhang, Qiang; Ye, Feng; Tian, Wei; ...

2017-06-12

Bilayered Sr 3Ru 2O 7 is an unusual metamagnetic metal with inherently antiferromagnetic (AFM) and ferromagnetic (FM) fluctuations. Partial substitution of Ru by Mn results in the establishment of a metal-insulator transition (MIT) at TMIT and AFM ordering at TM in Sr 3(Ru 1-xMn x) 2O 7. Using elastic neutron scattering, we investigated the effect of Mn doping on the magnetic structure, in-plane magnetic correlation lengths and their correlation to the MIT in Sr 3(Ru 1-xMn x) 2O 7 (x=0.06 and 0.12). With the increase of Mn doping (x) from 0.06 to 0.12 or the decrease of temperatures for x=0.12,more » an evolution from an in-plane short-range to long-range antiferromagnetic (AFM) ground state occurs. For both compounds, the magnetic ordering has a double-stripe configuration, and the onset of magnetic correlation with an anisotropic behavior coincides with the sharp rise in electrical resistivity and specific heat. Since it does not induce a measurable lattice distortion, the double-stripe antiferromagnetic order with anisotropic spin texture breaks symmetry from a C 4v crystal lattice to a C 2v magnetic sublattice. These observations shed light on an age-old question regarding the Slater versus Mott-type MIT.« less

Porous Mn-doped cobalt oxide@C nanocomposite: a stable anode material for Li-ion rechargeable batteries

NASA Astrophysics Data System (ADS)

Kalubarme, Ramchandra S.; Jadhav, Sarika M.; Kale, Bharat B.; Gosavi, Suresh W.; Terashima, Chiaki; Fujishima, Akira

2018-07-01

Cobalt oxide is a transition metal oxide, well studied as an electrode material for energy storage applications, especially in supercapacitors and rechargeable batteries, due to its high charge storage ability. However, it suffers from low conductivity, which effectively hampers its long-term stability. In the present work, a simple strategy to enhance the conductivity of cobalt oxide is adopted to achieve stable electrochemical performance by means of carbon coating and Mn doping, via a simple and controlled, urea-assisted glycine-nitrate combustion process. Structural analysis of carbon coated Mn-doped Co3O4 (Mn-Co3O4@C) confirms the formation of nanoparticles (∼50 nm) with connected morphology, exhibiting spinel structure. The Mn-Co3O4@C electrode displays superior electrochemical performance as a Li-ion battery anode, delivering a specific capacity of 1250 mAh g‑1. Mn-Co3O4@C demonstrates excellent performance in terms of long-term stability, keeping charge storage ability intact even at high current rates due to the synergistic effects of fast kinetics—provided by enriched electronic conductivity, which allows ions to move freely to active sites and electrons from reaction sites to substrate during redox reactions—and high surface area combined with mesoporous architecture. The fully assembled battery device using Mn-Co3O4@C and standard LiCoO2 electrode shows 90% capacity retention over 100 cycles.

Synthesis and characterization of Ca-doped LaMnAsO

NASA Astrophysics Data System (ADS)

Liu, Yong; Straszheim, Warren E.; Das, Pinaki; Islam, Farhan; Heitmann, Thomas W.; McQueeney, Robert J.; Vaknin, David

2018-05-01

We report on our attempt to hole-dope the antiferromagnetic semiconductor LaMnAsO by substitution of the La3 + site by Ca2 +. We use neutron and x-ray diffraction, magnetic susceptibility, and transport techniques to characterize polycrystalline (La1 -xCax)MnAsO samples prepared by solid-state reaction and find that the parent compound is highly resistant to substitution with an upper limit x ≤0.01 . Magnetic susceptibility of the parent and the x =0.002 (xnom=0.04 ) compounds indicate a negligible presence of magnetic impurities (i.e., MnO or MnAs). Rietveld analysis of neutron and x-ray diffraction data shows the preservation of both the tetragonal (P 4 /n m m ) structure upon doping and the antiferromagnetic ordering temperature, TN=355 ±5 K.

Nonplasmonic Hot-Electron Photocurrents from Mn-Doped Quantum Dots in Photoelectrochemical Cells.

PubMed

Dong, Yitong; Rossi, Daniel; Parobek, David; Son, Dong Hee

2016-03-03

We report the measurement of the hot-electron current in a photoelectrochemical cell constructed from a glass/ITO/Al2 O3 (ITO=indium tin oxide) electrode coated with Mn-doped quantum dots, where hot electrons with a large excess kinetic energy were produced through upconversion of the excitons into hot electron hole pairs under photoexcitation at 3 eV. In our recent study (J. Am. Chem. Soc. 2015, 137, 5549), we demonstrated the generation of hot electrons in Mn-doped II-VI semiconductor quantum dots and their usefulness in photocatalytic H2 production reaction, taking advantage of the more efficient charge transfer of hot electrons compared with band-edge electrons. Here, we show that hot electrons produced in Mn-doped CdS/ZnS quantum dots possess sufficient kinetic energy to overcome the energy barrier from a 5.4-7.5 nm thick Al2 O3 layer producing a hot-electron current in photoelectrochemical cell. This work demonstrates the possibility of harvesting hot electrons not only at the interface of the doped quantum dot surface, but also far away from it, thus taking advantage of the capability of hot electrons for long-range electron transfer across a thick energy barrier. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physical properties of antiferromagnetic Mn doped ZnO samples: Role of impurity phase

NASA Astrophysics Data System (ADS)

Neogi, S. K.; Karmakar, R.; Misra, A. K.; Banerjee, A.; Das, D.; Bandyopadhyay, S.

2013-11-01

Structural, morphological, optical, and magnetic properties of nanocrystalline Zn1-xMnxO samples (x=0.01, 0.02, 0.04, 0.06, 0.08 and 0.10) prepared by the sol-gel route are studied by X-ray diffraction (XRD), Scanning electron microscopy (SEM), UV-visible absorption spectroscopy, Superconducting quantum interference device (SQUID) magnetometry and positron annihilation lifetime spectroscopy (PALS). XRD confirms formation of wurzite structure in all the Mn-substituted samples. A systematic increase in lattice constants and decrease in grain size have been observed with increase in manganese doping concentration up to 6 at% in the ZnO structure. An impurity phase (ZnMnO3) has been detected when percentage of Mn concentration is 6 at% or higher. The optical band gap of the Mn-substituted ZnO samples decrease with increase in doping concentration of manganese whereas the width of the localized states increases. The antiferromagnetic exchange interaction is strong in the samples for 2 and 4 at% of Mn doping but it reduces when the doping level increases from 6 at% and further. Positron life time components τ1 and τ2 are found to decrease when concentration of the dopant exceeds 6 at%. The changes in magnetic properties as well as positron annihilation parameters at higher manganese concentration have been assigned as due to the formation of impurity phase. Single phase structure has been observed up to 6 at% of Mn doping. Impurity phase has been developed above 6 at% of Mn doping. Antiferromagnetic and paramagnetic interactions are present in the samples. Defect parameters show sharp fall as Mn concentration above 6 at%. The magnetic and defect properties are modified by the formation of impurity phase.

Efficient rare-earth free red-emitting Ca2YSbO6:Mn4+,M(M = Li+, Na+, K+, Mg2+) phosphors for white light-emitting diodes.

PubMed

Zhong, Jiasong; Chen, Daqin; Chen, Xiao; Wang, Keyuan; Li, Xinyue; Zhu, Yiwen; Ji, Zhenguo

2018-05-08

Owing to its low-cost and satisfactory luminescent-emission performance in warm white light-emitting diodes (w-LEDs), the non-rare-earth Mn4+-activated red phosphor has become a promising competitor of commercial rare-earth doped phosphor. In this study, a series of novel red-light emitting phosphors based on Ca2YSbO6:Mn4+ have been developed successfully by a conventional solid-state reaction. The structural and luminescent properties of these phosphors are systematically investigated. The as-prepared Ca2YSbO6:Mn4+ product exhibits a broad excitation band ranging from 250 to 600 nm and an abnormal intense deep-red emission centered at 680 nm with a full width at half maximum (FWHM) of ∼46 nm. The optimal Mn4+ doping concentration is about 0.3 mol%, and the concentration quenching mechanism is determined to be a dipole-dipole interaction. Impressively, the Ca2YSbO6:0.003Mn4+ phosphor shows an outstanding quantum efficiency of 62.6% and an excellent thermal stability. In addition, the effect of Li+, Mg2+, Na+ and K+ dopants on the luminescent properties of Mn4+-doped Ca2YSbO6 phosphors is elucidated. Furthermore, by employing the as-prepared Ca2YSbO6:Mn4+ as a red component, a warm w-LED with high color rendering index (Ra = 87.5) and low correlated color temperature (CCT = 3255 K) can be acquired. It is believed that the present phosphor has a potential application as a supplement of the red component for warm w-LEDs.

Critical exponent analysis of lightly germanium-doped La0.7Ca0.3Mn1-xGexO3 (x = 0.05 and x = 0.07)

NASA Astrophysics Data System (ADS)

Nanto, Dwi; Kurniawan, Budhy; Soegijono, Bambang; Ghosh, Nilotpal; Hwang, Jong-Soon; Yu, Seong-Cho

2018-04-01

We have used a critical behavior study of La0.7Ca0.3MnO3 (LCMO) manganite perovskites whose Mn sites have been doped with Ge to explore magnetic interactions. Light Ge doping of 5 or 7 percent tended to produce LCMOs with second order magnetic transitions. The critical parameters of 5- and 7-percent Ge-doped LCMO were determined to be TC = 185 K, β = 0.331 ± 0.019, and γ = 1.15 ± 0.017; and TC = 153 K, β = 0.496 ± 0.011, and γ = 1.03 ± 0.046, respectively, via the modified Arrott plot method. Isothermal magnetization data collected near the Curie temperature (TC) was split into a universal function with two branches M(H,ɛ) = |ɛ|βf±(H/|ɛ|β+γ), where ɛ=(T-TC)/TC is the reduced temperature. f+ is used when T>TC, while f̲ is used when T

Structural study of Co doped MnV2O4 from first principles

NASA Astrophysics Data System (ADS)

Krishna, Jyoti; Maitra, Tulika

2017-05-01

Inspired by the recent experiments, we have theoretically investigated the compound Mn1-xCoxV2O4 using first-principles density functional theory for x = 0.0, 0.25, 0.5, 0.75. On increasing Co doping on Mn site, chemical pressure on V-V bonds increases which make the system more itinerant as indicated by decrease in the calculated RV-V values with increasing x. The calculated band gap is also seen to decrease with increasing x. This Co-doping induced itinerancy facilitates superexchange interaction among Co and V ions leading to an increase in the magnetic transition temperature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuping, Duan, E-mail: duanyp@dlut.edu.c; Jia, Zhang; Hui, Jing

Fe-doped MnO{sub 2} with a hollow sea urchin-like ball chain shape was first synthesized under a high magnetic field of 10 T. The formation mechanism was investigated and discussed in detail. The synthesized samples were characterized by XRD, SEM, TEM, EMPA, and vector network analysis. By doping MnO{sub 2} with Fe, the relative complex permittivity of MnO{sub 2} and its corresponding loss tangent clearly decreases, but its relative complex permeability and its corresponding loss tangent markedly increases. Moreover, the theoretically calculated values of reflection loss show that with increasing the Fe content, the as-prepared Fe-doped MnO{sub 2} exhibits good microwavemore » absorption capability. -- Graphical Abstract: Fe-doped MnO{sub 2} with a hollow sea urchin-like ball chain shape was first synthesized in a high magnetic field of 10 T via a simple chemical process. Display Omitted Highlights: {yields} Fe-doped MnO{sub 2} with a hollow sea urchin-like ball chain shape was first synthesized. {yields} We investigated formation mechanism and electromagnetic properties of the Fe-doped MnO{sub 2}. {yields} By doping MnO{sub 2} with Fe, the electromagnetic properties are improved obviously.« less

Manganese modified structural and optical properties of zinc soda lime silica glasses.

PubMed

Samsudin, Nur Farhana; Matori, Khamirul Amin; Wahab, Zaidan Abdul; Fen, Yap Wing; Liew, Josephine Ying Chi; Lim, Way Foong; Mohd Zaid, Mohd Hafiz; Omar, Nur Alia Sheh

2016-03-20

A series of MnO-doped zinc soda lime silica glass systems was prepared by a conventional melt and quenching technique. In this study, the x-ray diffraction analysis was applied to confirm the amorphous nature of the glasses. Fourier transform infrared spectroscopy shows the glass network consists of MnO₄, SiO₄, and ZnO₄ units as basic structural units. The glass samples under field emission scanning electron microscopy observation demonstrated irregularity in shape and size with glassy phase-like structure. The optical absorption studies revealed that the optical bandgap (E_opt) values decrease with an increase of MnO content. Through the results of various measurements, the doping of MnO in the glass matrix had effects on the performance of the glasses and significantly improved the properties of the glass sample as a potential host for phosphor material.

Effects of Mn-doping on the giant magnetocaloric effect of EuTiO3 compound

NASA Astrophysics Data System (ADS)

Mo, Zhao-Jun; Sun, Qi-Lei; Han, Sheng; Zhao, Yun; Chen, Xing; Li, Lan; Liu, Guo-Dong; Meng, Fan-Bin; Shen, Jun

2018-06-01

The magnetic properties and magnetocaloric effect of EuTi1-xMnxO3 (x = 0-0.1) compounds are investigated. When the Ti4+ was substituted by Mn2+, the lattice constants were changed, the Eu3+ state and the oxygen vacancy generated. The exchange mechanisms were more complex among the Mn2+ 3d, the Eu 5d and Eu2+ 4f. The FM phase was dominant between AFM and FM as Mn substitute for Ti, which improve the MCE under low magnetic field. The values of -ΔSMmax are evaluated to 11.7 and 11.1 J/kg K for EuTi0.975Mn0.025O3 and EuTi0.95Mn0.05O3 compounds, under a magnetic field change of 1 T. And, the values of RC were obviously enhanced under the magnetic field changes of 1 and 2 T. Therefore, the giant reversible MCE makes these compounds promising candidates for magnetic refrigeration.

Crystallographic and magnetic properties of sol-gel synthesized T xCo 1-xFe 2O 4 (T=Mn and Cr) thin films

NASA Astrophysics Data System (ADS)

Kim, Kwang Joo; Kyung Kim, Hee; Ran Park, Young; Choi, Seung-li; Eun Kim, Sung; Jung Lee, Hee; Yun Park, Jae; Jin Kim, Sam

Effects of Mn and Cr substitution for Co on crystallographic and magnetic properties of inverse-spinel CoFe 2O 4 thin films were investigated. The crystal structure of the samples remain cubic for x<1 with the lattice constant ( a0) increasing with x for Mn doping and remaining constant for Cr doping. Tetrahedral Fe 2+ ions were detected in Cr xCo 1-xFe 2O 4 by Mössbauer spectroscopy while no such ions existed in Mn xCo 1-xFe 2O 4. The appearance of the tetrahedral Fe 2+ ions can be explained in terms of the Cr 3+ substitution for the octahedral Co 2+ sites with the resultant charge imbalance being compensated by a reduction of the tetrahedral Fe 3+ into Fe 2+. The observed variation in a0 and magnetic properties can be partly explained in terms of Mn 2+ and Cr 3+ substitution of octahedral sites in Mn xCo 1-xFe 2O 4 and Cr xCo 1-xFe 2O 4, respectively.

Synthesis and characterization of Ca-doped LaMnAsO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yong; Straszheim, Warren E.; Das, Pinaki

Here, we report on our attempt to hole-dope the antiferromagnetic semiconductor LaMnAsO by substitution of the La 3+ site by Ca 2+. We use neutron and x-ray diffraction, magnetic susceptibility, and transport techniques to characterize polycrystalline (La 1–xCa x)MnAsO samples prepared by solid-state reaction and find that the parent compound is highly resistant to substitution with an upper limit x ≤ 0.01. Magnetic susceptibility of the parent and the x = 0.002(x nom = 0.04) compounds indicate a negligible presence of magnetic impurities (i.e., MnO or MnAs). Rietveld analysis of neutron and x-ray diffraction data shows the preservation of bothmore » the tetragonal (P4/nmm) structure upon doping and the antiferromagnetic ordering temperature, T N = 355 ± 5 K.« less

Synthesis and characterization of Ca-doped LaMnAsO

DOE PAGES

Liu, Yong; Straszheim, Warren E.; Das, Pinaki; ...

2018-05-18

Here, we report on our attempt to hole-dope the antiferromagnetic semiconductor LaMnAsO by substitution of the La 3+ site by Ca 2+. We use neutron and x-ray diffraction, magnetic susceptibility, and transport techniques to characterize polycrystalline (La 1–xCa x)MnAsO samples prepared by solid-state reaction and find that the parent compound is highly resistant to substitution with an upper limit x ≤ 0.01. Magnetic susceptibility of the parent and the x = 0.002(x nom = 0.04) compounds indicate a negligible presence of magnetic impurities (i.e., MnO or MnAs). Rietveld analysis of neutron and x-ray diffraction data shows the preservation of bothmore » the tetragonal (P4/nmm) structure upon doping and the antiferromagnetic ordering temperature, T N = 355 ± 5 K.« less

One pot synthesis of ilmenite-type NiMnO3-"nitrogen-doped" graphene nanocomposite as next generation supercapacitors.

PubMed

Giri, Soumen; Ghosh, Debasis; Das, Chapal Kumar

2013-10-28

NiMnO3-nitrogen doped graphene composite has been synthesized by a simple hydrothermal method and its supercapacitor performance investigated. The composite exhibits a specific capacitance of 750.2 F g(-1) in 1 M Na2SO4 at a scan rate of 1 mV s(-1). Nitrogen insertion inside the carbon lattice plays a crucial role in the enhancement of the overall specific capacitance and its long-term stability. This reproducible and superior performance of NiMnO3-nitrogen doped graphene composite make it attractive as a candidate for energy storage materials.

THE EFFECT OF SI DOPING ON THE ELECTROCHEMICAL CHARACTERISTICS OF LiNixMnyCo(1-x-y)O2

NASA Astrophysics Data System (ADS)

Na, Seong-Hwan; Kim, Hyun-Soo; Moon, Seong-In

A new simple way of synthesizing Li[NiMnCo]O2 was contrived and its electrochemical characteristics were enhanced by Si doping using solution-based synthetic route. The newly synthesized Li[NiMnCo]O2 showed capacity of 175mAh/g and good cycle life at as high cut-off voltage as 4.5V. Si-doping improved the rate capability, specific capacity, and cycle life of the material through increasing lattice parameters and lowering electrochemical impedance.

Enhancement of tetragonal anisotropy and stabilisation of the tetragonal phase by Bi/Mn-double-doping in BaTiO3 ferroelectric ceramics

PubMed Central

Yabuta, Hisato; Tanaka, Hidenori; Furuta, Tatsuo; Watanabe, Takayuki; Kubota, Makoto; Matsuda, Takanori; Ifuku, Toshihiro; Yoneda, Yasuhiro

2017-01-01

To stabilise ferroelectric-tetragonal phase of BaTiO3, the double-doping of Bi and Mn up to 0.5 mol% was studied. Upon increasing the Bi content in BaTiO3:Mn:Bi, the tetragonal crystal-lattice-constants a and c shrank and elongated, respectively, resulting in an enhancement of tetragonal anisotropy, and the temperature-range of the ferroelectric tetragonal phase expanded. X-ray absorption fine structure measurements confirmed that Bi and Mn were located at the A(Ba)-site and B(Ti)-site, respectively, and Bi was markedly displaced from the centrosymmetric position in the BiO12 cluster. This A-site substitution of Bi also caused fluctuations of B-site atoms. Magnetic susceptibility measurements revealed a change in the Mn valence from +4 to +3 upon addition of the same molar amount of Bi as Mn, probably resulting from a compensating behaviour of the Mn at Ti4+ sites for donor doping of Bi3+ into the Ba2+ site. Because addition of La3+ instead of Bi3+ showed neither the enhancement of the tetragonal anisotropy nor the stabilisation of the tetragonal phase, these phenomena in BaTiO3:Mn:Bi were not caused by the Jahn-Teller effect of Mn3+ in the MnO6 octahedron, but caused by the Bi-displacement, probably resulting from the effect of the 6 s lone-pair electrons in Bi3+. PMID:28367973

Correlated vortex pinning in Si-nanoparticle doped MgB 2

NASA Astrophysics Data System (ADS)

Kušević, I.; Babić, E.; Husnjak, O.; Soltanian, S.; Wang, X. L.; Dou, S. X.

2004-12-01

The magnetoresistivity and critical current density of well characterized Si-nanoparticle doped and undoped Cu-sheathed MgB 2 tapes have been measured at temperatures T≥28 K in magnetic fields B≤0.9 T. The irreversibility line Birr( T) for doped tape shows a stepwise variation with a kink around 0.3 T. Such Birr( T) variation is typical for high-temperature superconductors with columnar defects (a kink occurs near the matching field Bϕ) and is very different from a smooth Birr( T) variation in undoped MgB 2 samples. The microstructure studies of nanoparticle doped MgB 2 samples show uniformly dispersed nanoprecipitates, which probably act as a correlated disorder. The observed difference between the field variations of the critical current density and pinning force density of the doped and undoped tape supports the above findings.

Structural and electrochemical properties of the doped spinels Li 1.05M 0.02Mn 1.98O 3.98N 0.02 (M = Ga 3+, Al 3+, or Co 3+; N = S 2- or F -) for use as cathode material in lithium batteries

NASA Astrophysics Data System (ADS)

Amaral, Fábio A.; Bocchi, Nerilso; Brocenschi, Ricardo F.; Biaggio, Sonia R.; Rocha-Filho, Romeu C.

The doped and milled spinels Li 1.05M 0.02Mn 1.98O 3.98N 0.02 (M = Ga 3+, Al 3+ or Co 3+; N = S 2- or F -) are studied aiming at obtaining an improved charge/discharge cycling performance. These spinels are prepared by a solid-state reaction among the precursors ɛ-MnO 2, LiOH, and the respective oxide/salt of the doping ions at 750 °C for 72 h and milled for 30 min. The obtained spinels are characterized by XRD, SEM, and determinations of the average manganese valence n. In the charge and discharge tests, the doped spinels present outstanding initial values of the specific discharge capacity C (117-126 mA h g -1), decreasing in the following order: C(Li 1.05Al 0.02Mn 1.98S 3.02O 3.98) > C(Li 1.05Al 0.02Mn 1.98F 3.02O 3.98) > C(Li 1.05Ga 0.02Mn 1.98S 3.02O 3.98) > C(Li 1.05Ga 0.02Mn 1.98F 3.02O 3.98) > C(Li 1.05Co 0.02Mn 1.98S 3.02O 3.98) > C(Li 1.05Co 0.02Mn 1.98F 3.02O 3.98). The doped spinel Li 1.05Ga 0.02Mn 1.98S 3.02O 3.98 presents an excellent electrochemical performance, with a low capacity loss even after 300 charge and discharge cycles (from 120 to 115 mA h g -1 or 4%).

Synthesis and Characterization of ZNO/MN Nanocomposite by using Sol-Gel Method

NASA Astrophysics Data System (ADS)

Ningsih, S. K. W.; Bahrizal, B.; Nasra, E.; Nizar, U. K.; Farisya, R.

2018-04-01

Zink oxide doped Mn nanocomposites were synthesized by simple sol-gel method at low temperature by using combination of aquadest with methanol as the solvent and ethylene glycol as the additive. Zink acetate dehydrate and manganese chloride tetrahydrate were used as the precursors. Composition dopants were 1,3,5,and 7%. The crystals were formed by drying at 110°C for 1 hour, after which they were heated at ± 500°C for 2 hours. The as-prepared ZnO/Mn nanocomposites were characterized by X-ray diffraction (XRD) and UV Diffuse Reflectance Spectrometer (UVDRS). The XRD patterns of the ZnO nanocrystals showed that they are mostly hexagonal wurtzite with specific peaks at 2θ = 31, 34, 36, 47, 56, 63, 66 dan 69. The sizes of the ZnO doped Mn particles produced with 1%, 3%, 5% and 7% were18-95; 17-87; 18-96 19-98 nm, respectively. UVDRS analysis showed that the band gap of the ZnO were 2,60; 2,90; 2,99 dan 3,01 eV for 1%, 3%, 5% and 7% Mn respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lecointre, A., E-mail: lecointre.aurelie@gmail.com; Bessière, A., E-mail: aurelie-bessiere@chimie-paristech.fr; Department of Physics, Goa University, Taleigao Plateau, Goa 403 206

Highlights: ► Long-lasting phosphorescence of CaMgSi{sub 2}O{sub 6}:Mn is studied for bioimaging application. ► CaMgSi{sub 2}O{sub 6}:Mn yields orange and red luminescence of Mn{sup II}{sub Ca} and Mn{sup II}{sub Mg}, respectively. ► Red Mn{sup II}{sub Mg} emission dominates long-lasting phosphorescence spectra. ► Mn mainly substitutes Mg. ► Mn{sup II}{sub Mg} plays the role of hole trap in the persistent luminescence mechanism. - Abstract: Materials with red long-lasting phosphorescence, such as Mn{sup II}-doped diopsides, can be used for small animal in vivo imaging. CaMgSi{sub 2}O{sub 6}:Mn powders with various amounts of Mn were prepared by sol–gel to investigate their long-lasting phosphorescencemore » mechanism. X-ray diffraction, X-ray absorption fine and near-edge structure and electron paramagnetic resonance showed that manganese is quantitatively introduced in the structure as Mn{sup II}. Most of the Mn doping ions substitute Mg and possess a highly elongated octahedral environment. While photoluminescence and X-ray excited optical luminescence spectra show both orange (585 nm) and red (685 nm) {sup 4}T{sub 1} ({sup 4}G) → {sup 6}A{sub 1} ({sup 6}S) emission of Mn{sup II}{sub Ca} and Mn{sup II}{sub Mg}, respectively, Mn{sup II}{sub Mg} red emission dominates long-lasting phosphorescence and thermally stimulated luminescence spectra. These results point to Mn{sup II}{sub Mg} as the preferential hole trap and recombination center in the long-lasting phosphorescence mechanism. An intense persistent red emission suitable for in vivo imaging probes is obtained for the highest nominal Mn content (7.5%)« less

Novel room temperature ferromagnetic semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Amita

2004-06-01

Today's information world, bits of data are processed by semiconductor chips, and stored in the magnetic disk drives. But tomorrow's information technology may see magnetism (spin) and semiconductivity (charge) combined in one 'spintronic' device that exploits both charge and 'spin' to carry data (the best of two worlds). Spintronic devices such as spin valve transistors, spin light emitting diodes, non-volatile memory, logic devices, optical isolators and ultra-fast optical switches are some of the areas of interest for introducing the ferromagnetic properties at room temperature in a semiconductor to make it multifunctional. The potential advantages of such spintronic devices will bemore » higher speed, greater efficiency, and better stability at a reduced power consumption. This Thesis contains two main topics: In-depth understanding of magnetism in Mn doped ZnO, and our search and identification of at least six new above room temperature ferromagnetic semiconductors. Both complex doped ZnO based new materials, as well as a number of nonoxides like phosphides, and sulfides suitably doped with Mn or Cu are shown to give rise to ferromagnetism above room temperature. Some of the highlights of this work are discovery of room temperature ferromagnetism in: (1) ZnO:Mn (paper in Nature Materials, Oct issue, 2003); (2) ZnO doped with Cu (containing no magnetic elements in it); (3) GaP doped with Cu (again containing no magnetic elements in it); (4) Enhancement of Magnetization by Cu co-doping in ZnO:Mn; (5) CdS doped with Mn, and a few others not reported in this thesis. We discuss in detail the first observation of ferromagnetism above room temperature in the form of powder, bulk pellets, in 2-3 mu-m thick transparent pulsed laser deposited films of the Mn (<4 at. percent) doped ZnO. High-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) spectra recorded from 2 to 200nm areas showed homogeneous distribution of Mn substituting for Zn a 2 + state in the ZnO lattice. Ferromagnetic Resonance (FMR) technique is used to confirm the existence of ferromagnetic ordering at temperatures as high as 425K. The ab initio calculations were found to be consistent with the observation of ferromagnetism arising from fully polarized Mn 2 + state. The key to observed room temperature ferromagnetism in this system is the low temperature processing, which prevents formation of clusters, secondary phases and the host ZnO from becoming n-type. The electronic structure of the same Mn doped ZnO thin films studied using XAS, XES and RIXS, revealed a strong hybridization between Mn 3d and O 2p states, which is an important characteristic of a Dilute magnetic Semiconductor (DMS). It is shown that the various processing conditions like sintering temperature, dopant concentration and the properties of precursors used for making of DMS have a great influence on the final properties. Use of various experimental techniques to verify the physical properties, and to understand the mechanism involved to give rise to ferromagnetism is presented. Methods to improve the magnetic moment in Mn doped ZnO are also described. New promising DMS materials (such as Cu doped ZnO are explored). The demonstrated new capability to fabricate powder, pellets, and thin films of room temperature ferromagnetic semiconductors thus makes possible the realization of a wide range of complex elements for a variety of new multifunctional phenomena related to Spintronic devices as well as magneto-optic components.« less

Synthesis and characterization of reduced graphene oxide decorated with CeO2-doped MnO2 nanorods for supercapacitor applications.

PubMed

Ojha, Gunendra Prasad; Pant, Bishweshwar; Park, Soo-Jin; Park, Mira; Kim, Hak-Yong

2017-05-15

A novel and efficient CeO 2 -doped MnO 2 nanorods decorated reduced graphene oxide (CeO 2 -MnO 2 /RGO) nanocomposite was successfully synthesized via hydrothermal method. The growth of the CeO 2 doped MnO 2 nanorods over GO sheets and reduction of GO were simultaneously carried out under hydrothermal treatment. The morphology and structure of as-synthesized nanocomposite were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy, which revealed the formation of CeO 2 -MnO 2 decorated RGO nanocomposites. The electrochemical performance of as-prepared CeO 2 -MnO 2 /RGO nanocomposites as an active electrode material for supercapacitor was evaluated by cyclic voltammetry, charge-discharge, and electrochemical impedance spectroscopy (EIS) methods in 2M alkaline medium. The obtained results revealed that as-synthesized CeO 2 -MnO 2 /RGO nanocomposite exhibited higher specific capacitance (648F/g) as compared to other formulations (MnO 2 /RGO nanocomposites: 315.13 F/g and MnO 2 nanorods: 228.5 F/g) at the scan rate of 5mV/s. After 1000 cycles, it retained ∼90.4%, exhibiting a good stability. The high surface area, enhanced electrical conductivity, and good stability possess by the nanocomposite make this material a promising candidate to be applied as a supercapacitor electrode. Copyright © 2017 Elsevier Inc. All rights reserved.

Magnetic and magnetotransport properties of the orthorhombic perovskites (Lu,Ca)MnO3

NASA Astrophysics Data System (ADS)

Imamura, N.; Karppinen, M.; Motohashi, T.; Yamauchi, H.

2008-01-01

Here we extend the research of the (R,Ca)MnO3 perovskites to the smallest- R end member (Lu,Ca)MnO3 . Magnetic and magnetotransport properties of the (Lu1-xCax)MnO3 system are systematically investigated in regard to carrier doping. It is found that hole doping into the antiferromagnetic x=0.0 phase, LuMnO3 , causes a spin-glass-like magnetic competition in the wide doping range of 0.1≤x≤0.6 , whereas electron doping into the antiferromagnetic x=1.0 phase, CaMnO3 , induces a large magnetoresistance effect for 0.8≤x≤0.95 .

Crystal structure and thermoelectric properties of Sr-Mo substituted CaMnO3: a combined experimental and computational study.

PubMed

Srivastava, D; Azough, F; Freer, R; Combe, E; Funahashi, R; Kepaptsoglou, D M; Ramasse, Q M; Molinari, M; Yeandel, S R; Baran, J D; Parker, S C

2015-12-21

A combination of experimental and computational techniques has been employed to study doping effects in perovskite CaMnO 3 . High quality Sr-Mo co-substituted CaMnO 3 ceramics were prepared by the conventional mixed oxide route. Crystallographic data from X-ray and electron diffraction showed an orthorhombic to tetragonal symmetry change on increasing the Sr content, suggesting that Sr widens the transition temperature in CaMnO 3 preventing phase transformation-cracking on cooling after sintering, enabling the fabrication of high density ceramics. Atomically resolved imaging and analysis showed a random distribution of Sr in the A-site of the perovskite structure and revealed a boundary structure of 90° rotational twin boundaries across {101} orthorhombic ; the latter are predominant phonon scattering sources to lower the thermal conductivity as suggested by molecular dynamics calculations. The effect of doping on the thermoelectric properties was evaluated. Increasing Sr substitution reduces the Seebeck coefficient but the power factor remains high due to improved densification by Sr substitution. Mo doping generates additional charge carriers due to the presence of Mn 3+ in the Mn 4+ matrix, reducing electrical resistivity. The major impact of Sr on thermoelectric behaviour is the reduction of the thermal conductivity as shown experimentally and by modelling. Strontium containing ceramics showed thermoelectric figure of merit ( ZT ) values higher than 0.1 at temperatures above 850 K. Ca 0.7 Sr 0.3 Mn 0.96 Mo 0.04 O 3 ceramics exhibit enhanced properties with S 1000K = -180 μV K -1 , ρ 1000K = 5 × 10 -5 Ωm, k 1000K = 1.8 W m -1 K -1 and ZT ≈ 0.11 at 1000 K.

Interplay of local structure, charge, and spin in bilayered manganese perovskites

NASA Astrophysics Data System (ADS)

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz; Kapusta, Czesław; Mitchell, John F.

2018-03-01

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. Here, we show results of high-energy resolution x-ray absorption and emission spectroscopies on a La2 -2 xSr1 +2 xMn2O7 family of bilayered manganites in a broad doping range (0.5 ≤x ≤1 ). We established a relation between local Mn charge and Mn-O distances as a function of doping. Based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.

Doped SnO₂ transparent conductive multilayer thin films explored by continuous composition spread.

PubMed

Lee, Jin Ju; Ha, Jong-Yoon; Choi, Won-Kook; Cho, Yong Soo; Choi, Ji-Won

2015-04-13

Mn-doped SnO₂ thin films were fabricated by a continuous composition spread (CCS) method on a glass substrate at room temperature to find optimized compositions. The fabricated materials were found to have a lower resistivity than pure SnO₂ thin films because of oxygen vacancies generated by Mn doping. As Mn content was increased, resistivity was found to decrease for limited doping concentrations. The minimum thin film resistivity was 0.29 Ω-cm for a composition of 2.59 wt % Mn-doped SnO₂. The Sn-O vibrational stretching frequency in FT-IR showed a blue shift, consistent with oxygen deficiency. Mn-doped SnO₂/Ag/Mn-doped SnO₂ multilayer structures were fabricated using this optimized composition deposited by an on-axis radio frequency (RF) sputter. The multilayer transparent conducting oxide film had a resistivity of 7.35 × 10⁻⁵ Ω-cm and an average transmittance above 86% in the 550 nm wavelength region.

Room temperature ferromagnetism in Mn-doped NiO nanoparticles

NASA Astrophysics Data System (ADS)

Layek, Samar; Verma, H. C.

2016-01-01

Mn-doped NiO nanoparticles of the series Ni1-xMnxO (x=0.00, 0.02, 0.04 and 0.06) are successfully synthesized using a low temperature hydrothermal method. Samples up to 6% Mn-doping are single phase in nature as observed from powder x-ray diffraction (XRD) studies. Rietveld refinement of the XRD data shows that all the single phase samples crystallize in the NaCl like fcc structure with space group Fm-3m. Unit cell volume decreases with increasing Mn-doping. Pure NiO nanoparticles show weak ferromagnetism, may be due to nanosize nature. Introduction of Mn within NiO lattice improves the magnetic properties significantly. Room temperature ferromagnetism is found in all the doped samples whereas the magnetization is highest for 2% Mn-doping and then decreases with further doping. The ZFC and FC branches in the temperature dependent magnetization separate well above 350 K indicating transition temperature well above room temperature for 2% Mn-doped NiO Nanoparticle. The ferromagnetic Curie temperature is found to be 653 K for the same sample as measured by temperature dependent magnetization study using vibrating sample magnetometer (VSM) in high vacuum.

Competing exchanges and spin-phonon coupling in Eu(1-x)R(x)MnO3 (R=Y, Lu).

PubMed

Mota, D A; Barcelay, Y Romaguera; Tavares, P B; Chaves, M R; Almeida, A; Oliveira, J; Ferreira, W S; Moreira, J Agostinho

2013-06-12

This work is focused on the phase diagrams and physical properties of Y-doped and Lu-doped EuMnO3. The differences in the corresponding phase boundaries in the (x,T) phase diagram could be overcome by considering a scaling of the Y(3+) and Lu(3+) concentrations to the tolerance factor. This outcome evidences that the tolerance factor is in fact a more reliable representative of the lattice deformation induced by doping. The normalization of the phase boundaries using the tolerance factor corroborates previous theoretical outcomes regarding the key role of competitive FM and AFM exchanges in determining the phase diagrams of manganite perovskites. However, significant differences in the nature and number of phases at low temperatures and concentrations could not be explained by just considering the normalization to the tolerance factor. The vertical phase boundary observed just for Lu-doped EuMnO3, close to 10% Lu, is understood by considering a low temperature Peierls-type spin-phonon coupling, which stabilizes the AFM-4 phase in Lu-doped EuMnO3.

Internal energy transfer phenomenon and light-emission properties of γ-LiAlO2 phosphor doped with Mn2+

NASA Astrophysics Data System (ADS)

Wang, Bai-Bin; Chang, Chi-Fen; Yang, Wein-Duo

2013-07-01

γ-LiAlO2:Mn2+ phosphor was synthesized using the cellulose-citric acid sol-gel method, and its light emission and energy transfer properties were investigated. Excitation and emission spectrum analysis revealed a decrease in intensity of the spectrum as the amount of Mn2+ doping increased. Blasse's equation determined the maximum distance for energy transfer between Mn2+ ions as 4.3142 nm. Dexter's theory verifies that the mechanism of energy transfer between Mn2+ ions conforms to an electric dipole and electric quadrupole interaction.

Ex-situ manufacturing of SiC-doped MgB2 used for superconducting wire in medical device applications

NASA Astrophysics Data System (ADS)

Herbirowo, Satrio; Imaduddin, Agung; Sofyan, Nofrijon; Yuwono, Akhmad Herman

2017-02-01

Magnesium diboride (MgB2) is a superconductor material with a relatively high critical temperature. Due to its relatively high critical temperature, this material is promising and has the potential to replace Nb3Sn for wire superconducting used in many medical devices. In this work, nanoparticle SiC-doped MgB2 superconducting material has been fabricated through an ex-situ method. The doping of nanoparticle SiC by 10 and 15 wt% was conducted to analyze its effect on specific resistivity of MgB2. The experiment was started by weighing a stoichiometric amount of MgB2 and nanoparticles SiC. Both materials were mixed and grounded for 30 minutes by using an agate mortar. The specimens were then pressed into a 6 mm diameter stainless steel tube, which was then reduced until 3 mm through a wire drawing method. X-ray diffraction analysis was conducted to confirm the phase, whereas the superconductivity of the specimens was analyzed by using resistivity measurement under cryogenic magnetic system. The results indicated that the commercial MgB2 showed a critical temperature of 37.5 K whereas the SiC doped MgB2 has critical temperature of 38.3 K.

Hydrostatic pressure effect on the spin reorientation transition of ferromagnetic Sm0.7-xLaxSr0.3MnO3 (x = 0, 0.1) polycrystals

NASA Astrophysics Data System (ADS)

Thiyagarajan, R.; Arumugam, S.; Sivaprakash, P.; Kannan, M.; Saravanan, C.; Yang, Wenge

2017-06-01

The hydrostatic pressure effect on the resistivity and magnetization of the narrow band gap manganite Sm0.7-xLaxSr0.3MnO3 (x = 0, 0.1) systems has been investigated. At ambient pressure measurements, the parent compound Sm0.7Sr0.3MnO3 showed a ferromagnetic-insulating nature, whereas the 10% La-doped compound Sm0.6La0.1Sr0.3MnO3 showed a ferromagnetic-metallic nature. Furthermore, both samples showed a spin-reorientation transition (TSR) below Curie temperature, which originated from the Mn sublattice and was supported by an antiferromagnetic Sm(4f)-Mn(3d) interaction. Both samples exhibited a normal and inverse magnetocaloric effect as a result of these two different magnetic transitions. Magnetization measurements on Sm0.7Sr0.3MnO3 under pressure did not show an appreciable change in the Curie temperature, but enhanced TSR, whereas an insulator-metallic transition was observed during resistivity measurements under pressure. On the other hand, for Sm0.6La0.1Sr0.3MnO3, TC increased and TSR reduced upon the application of pressure. The metallic nature which is observed at ambient pressure resistivity measurement was further enhanced with 97% of piezoresistance. The pressure did not change the normal magnetocaloric effect of Sm0.7Sr0.3MnO3, but increased it in Sm0.6La0.1Sr0.3MnO3. However, there was not much change in the inverse magnetocaloric effect of both compounds. These studies were analyzed based on the pressure effect on the activation energy and scattering interaction factors.

Chromium doping effects on structural and dielectric properties of Mn-Zn cobaltites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yadav, A.; Department of Physics, MEDICAPS Institute of Science and Technology, Pithampur 45331; Dar, Mashkoor A., E-mail: darmashkoor.phst@gmail.com

2016-05-06

The effect of transition metal Cr{sup 2+} ion as a dopant of Zn{sup 2+} in Mn{sub 0.5}Zn{sub 0.5}Co{sub 2}O{sub 4} is investigated. Co-doped Mn{sub 0.5}Zn{sub 0.5-x}Cr{sub x}Co{sub 2}O{sub 4} (x = 0, 0.3 and 0.5) cobaltites were prepared by solid-state reaction route. X-ray powder diffraction (XRD) analysis reveals that the samples prepared are polycrystalline single-phase cubic spinel in structure having a space group Fd3m. An increase in average particle size observed with Cr{sup 2+} doping. However other structural parameters such as X-ray density, micro strain and dislocation density shows almost a similar decreasing trend with increase in Cr{sup 2+}. Highmore » value of permittivity ∼10{sup 5} is observed for the parent Mn{sub 0.5}Zn{sub 0.5}Co{sub 2}O{sub 4} and shows a substantial decrease with increase in the Cr{sup 2+} doping. Higher doping of Cr{sup 2+} also increases the dielectric loss and hence limits its technological importance. At lower frequencies ac conductivity has been found to increase with increase in Cr{sup 2+} content.« less

Enhancement of electrochemical performance by simultaneous substitution of Ni and Mn with Fe in Ni-Mn spinel cathodes for Li-ion batteries

NASA Astrophysics Data System (ADS)

Kiziltas-Yavuz, Nilüfer; Yavuz, Murat; Indris, Sylvio; Bramnik, Natalia N.; Knapp, Michael; Dolotko, Oleksandr; Das, Bijoy; Ehrenberg, Helmut; Bhaskar, Aiswarya

2016-09-01

LiNi0.5-xFe2xMn1.5-xO4 (x = 0, 0.1, 0.15, 0.2) spinel cathode materials are synthesized using citric acid-assisted sol-gel method with final calcination temperature of 1000 °C. The structure and morphology of the materials are characterized by using synchrotron and neutron powder diffraction as well as scanning electron microscopy. Different from the parent LiNi0.5Mn1.5O4 (LNMO) material, the Fe-doped spinels do not contain a rock-salt type impurity phase. However, they contain additional layered (C2/m) and spinel Fe3O4 (Fd 3 bar m) phases in small amounts. The substitution of Fe into the spinel structure has been confirmed by Mössbauer spectroscopy. The Fe-doped spinels exhibit improved cycling stability (with a C/2 charge-discharge rate) and rate capability compared to the parent LNMO at room temperature in a voltage range 3.5-5.0 V. Among all these samples, the composition LiNi0.4Fe0.2Mn1.4O4 shows the best room temperature cycling stability (capacity retention of 92% after 300 cycles) as well as the highest initial discharge capacity (134 mAh g-1). The delivered capacities at high C-rates (especially at 10C and 20C) with respect to the capacity delivered at C/2 are higher for all Fe-doped samples compared to the parent LNMO. Furthermore, Fe-doping improves the thermal stability of the Ni-Mn spinels in the delithiated state.

Reinforcement of double-exchange ferromagnetic coupling by Ru in La{sub 1.24}Sr{sub 1.76}Mn{sub 2-y}Ru{sub y}O{sub 7} manganite system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumaresavanji, M., E-mail: vanji.hplt@gmail.com; Fontes, M.B.; Lopes, A.M.L.

2014-03-01

Highlights: • Effect of Mn-site doping by Ru has been studied in La{sub 1.24}Sr{sub 1.76}Mn{sub 2-y}Ru{sub y}O{sub 7}. • Electrical resistance, magnetoresistance and magnetic properties were measured. • Ru substitution enhances the ferromagnetism and metallicity. • Results were interpreted by the ferromagnetically coupled Ru with Mn ions in Mn–O–Ru network. - Abstract: The effect of Mn-site doping on magnetic and transport properties in the bilayer manganites La{sub 1.24}Sr{sub 1.76}Mn{sub 2-y}Ru{sub y}O{sub 7} (y = 0.0, 0.04, 0.08 and 0.15) has been studied. The undoped compound La{sub 1.24}Sr{sub 1.76}Mn{sub 2}O{sub 7} exhibits a ferromagnetic metal to paramagnetic insulator transition at T{submore » C} = 130 K and the substitution of Ru shifts the transition temperatures to higher temperature values. The increased metal–insulator transition by Ru substitution, obtained from temperature dependence of resistivity measurements, indicates that the Ru substitution enhances the metallic state at low temperature regime and favours the Mn–Ru pairs in the Ru doped samples. Moreover, the activation energy values calculated from the temperature dependence of resistivity curves suggest that the Ru substitution weakens the formation of polarons. The increased magnetoresistance ratio from 108% to 136% by Ru substitution, measured at 5 K, points out that the Ru substitution also enhances the inter-grain tunneling magnetoresistance. Thus, the ferromagnetic order and metallic state in La{sub 1.24}Sr{sub 1.76}Mn{sub 2}O{sub 7} system have been enhanced by the presence of Ru in the Mn-site. These reinforcements of ferromagnetic metallic state and magnetoresistance have been interpreted by the ferromagnetically coupled high spin states of Ru with Mn ions in the Mn–O–Ru network.« less

Influence of Oxygen Stoichiometry Variations on the Properties of CaMnO3 thin films

NASA Astrophysics Data System (ADS)

Goehringer, Tyler; Yong, Grace; Otouloumougoye, Brenda; Keshavarz, Camron; Sharma, Prahash; Tanyi, E. Kevin; Schaefer, David; Kolagani, Rajeswari

2013-03-01

The family of alkaline-earth doped rare earth manganese oxides RE1-xAExMnO3 exhibit a rich variety of electronic phases depending on the cation stoichiometry. In thin films of these materials, the oxygen stoichiometry is also a variable, and together with cation stoichiometry is known to play a key role in determining the equilibrium phase. The cation and oxygen stoichiometry variations influence electrical and magnetic properties through changes in the mixed valence state of Mn, i.e. the ratio of Mn3+ to Mn4+ ions. CaMnO3 is one of the end members of this family with x =1. Stoichiometric CaMnO3 is a canted antiferromagnetic insulator with the Mn ion in the Mn4+ valence state. We will present our results on the effects of oxygen content variation on the structural, electrical, and magnetoresistive properties CaMnO3 thin films grown by Pulsed Laser Deposition. These results will be compared to the effects of oxygen stoichiometry variation in thin films of its doped counter-part La1-xCaxMnO3. We will also discuss surface morphology changes associated with variation in oxygen stoichiometry which may be associated with different surface terminations. We acknowledge support from the NSF grant ECCS 1128586 at Towson University.

Manganese oxide nanowires wrapped with nitrogen doped carbon layers for high performance supercapacitors.

PubMed

Li, Ying; Mei, Yuan; Zhang, Lin-Qun; Wang, Jian-Hai; Liu, An-Ran; Zhang, Yuan-Jian; Liu, Song-Qin

2015-10-01

In this study, manganese oxide nanowires wrapped by nitrogen-doped carbon layers (MnO(x)@NCs) were prepared by carbonization of poly(o-phenylenediamine) layer coated onto MnO2 nanowires for high performance supercapacitors. The component and structure of the MnO(x)@NCs were controlled through carbonization procedure under different temperatures. Results demonstrated that this composite combined the high conductivity and high specific surface area of nitrogen-doped carbon layers with the high pseudo-capacitance of manganese oxide nanowires. The as-prepared MnO(x)@NCs exhibited superior capacitive properties in 1 M Na2SO4 aqueous solution, such as high conductivity (4.167×10(-3) S cm(-1)), high specific capacitance (269 F g(-1) at 10 mV s(-1)) and long cycle life (134 F g(-1) after 1200 cycles at a scan rate of 50 mV s(-1)). It is reckoned that the present novel hybrid nanowires can serve as a promising electrode material for supercapacitors and other electrochemical devices. Copyright © 2015 Elsevier Inc. All rights reserved.

Enhanced persistent red luminescence in Mn2+-doped (Mg,Zn)GeO3 by electron trap and conduction band engineering

NASA Astrophysics Data System (ADS)

Katayama, Yumiko; Kayumi, Tomohiro; Ueda, Jumpei; Tanabe, Setsuhisa

2018-05-01

The effect of Zn substitution on the persistent luminescence properties of MgGeO3:Mn2+-Ln3+ (Ln = Eu and Yb) red phosphors was investigated. The intensity of the persistent luminescence of the Eu3+ co-doped phosphors increased with increasing Zn content, whereas that of the Yb3+ co-doped samples decreased. For both series of lanthanide co-doped samples, the thermoluminescence (TL) glow peak shifted to the lower temperature side with increasing Zn content. These persistent luminescence properties were well explained in terms of lowering of the bottom of the conduction band relative to the ground state of the divalent lanthanide ions. Especially, in Eu3+ co-doped system, TL peak shifted from 520 K to 318 K by 50% Zn substitution. The persistent radiance of the (Mg0.5 Zn0.5)GeO3: Mn2+-Eu3+ sample at 1 h after ceasing UV light was 46 times stronger than that of MgGeO3:Mn2+-Eu3+, and 11 times stronger than that of ZnGa2O4: Cr3+ standard deep red persistent phosphor.

Co and Fe doping effect on negative temperature coefficient characteristics of nano-grained NiMn2O4 thick films fabricated by aerosol-deposition.

PubMed

Ryu, Jungho; Han, Guifang; Lee, Jong-Pil; Lim, Dong-Soo; Park, Yun-Soo; Jeong, Dae-Yong

2013-05-01

Spinel structured highly dense NiMn2O4-based (NMO) negative temperature coefficient (NTC) thermistor thick films were fabricated by aerosol-deposition at room temperature. To enhance the thermistor B constant, which represents the temperature sensitivity of the NMO thermistor material, Co and Co-Fe doping was applied. In the case of single element doping of Co, 5 mol% doped NMO showed a high B constant of over 5000 K, while undoped NMO showed -4000 K. By doping Fe to the 5 mol% Co doped NMO, the B constant was more enhanced at over 5600 K. The aging effect on the NTC characteristics of Co doped and Fe-Co co-doped NMO thick film showed very stable resistivity-time characteristics because of the highly dense microstructure.

Atomistic simulation and XAS investigation of Mn induced defects in Bi{sub 12}TiO{sub 20}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rezende, Marcos V dos S.; Santos, Denise J.; Jackson, Robert A.

2016-06-15

This work reports an investigation of the valence and site occupancy of Mn dopants in Bi{sub 12}TiO{sub 20} (BTO: Mn) host using X-ray Absorption (XAS) and atomistic simulation techniques based on energy minimisation. X-ray Absorption Near Edge Structure (XANES) at the Mn K-edges gave typical results for Mn ions with mixed valences of 3+ and 4+. Extended X-ray Absorption Fine Structure (EXAFS) results indicated that Mn ions are probably substituted at Ti sites. Atomistic simulation was performed assuming the incorporation of Mn{sup 2+}, Mn{sup 3+} and Mn{sup 4+} ions at either Bi{sup 3+} or Ti{sup 4+} sites, and the resultsmore » were compared to XANES and EXAFS measurements. Electrical conductivity for pure and doped samples was used to evaluate the consistency of the proposed model. - Graphical abstract: The structure of Bi{sub 12}TiO{sub 20} (BTO). Display Omitted - Highlights: • Pure and Mn-doped Bi{sub 12}TiO{sub 20} samples were studied by experimental techniques combined with atomistic simulation. • Good agreement between experimental and simulation results was obtained. • XANES results suggest a mixture of 3+ and 4+ valences for Mn, occupying the Ti4+ site in both cases. • Charge compensation by holes is most energetically favoured, explaining the enhancement observed in AC dark conductivity.« less

Effect of Zn doping on the magneto-caloric effect and critical constants of Mott insulator MnV{sub 2}O{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shahi, Prashant; Kumar, A.; Shukla, K. K.

2014-09-15

X-ray absorption near edge spectra (XANES) and magnetization of Zn doped MnV{sub 2}O{sub 4} have been measured and from the magnetic measurement the critical exponents and magnetocaloric effect have been estimated. The XANES study indicates that Zn doping does not change the valence states in Mn and V. It has been shown that the obtained values of critical exponents β, γ and δ do not belong to universal class and the values are in between the 3D Heisenberg model and the mean field interaction model. The magnetization data follow the scaling equation and collapse into two branches indicating that themore » calculated critical exponents and critical temperature are unambiguous and intrinsic to the system. All the samples show large magneto-caloric effect. The second peak in magneto-caloric curve of Mn{sub 0.95}Zn{sub 0.05}V{sub 2}O{sub 4} is due to the strong coupling between orbital and spin degrees of freedom. But 10% Zn doping reduces the residual spins on the V-V pairs resulting the decrease of coupling between orbital and spin degrees of freedom.« less

Synthesis, properties, and formation mechanism of Mn-doped Zn 2 SiO 4 nanowires and associated heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Haiqing; Moronta, Dominic; Li, Luyao

In this study, we have put forth a facile hydrothermal approach to synthesize an array of one-dimensional (1D) Mn-doped Zn 2SiO 4 nanostructures. Specifically, we have probed and correlated the effects of controllable reaction parameters such as the pH and Mn dopant concentrations with the resulting crystal structures and morphologies of the products obtained. Based upon our results, we find that careful tuning of the pH versus the Mn dopant level gives rise to opposite trends with respect to the overall size of the resulting one-dimensional nanostructures. Significantly, we have highlighted the role of the Mn dopant ion concentration asmore » a potentially generalizable reaction parameter in solution-based synthesis for controlling morphology and hence, the observed optical behavior. Indeed, such a strategy can be potentially generalized to systems such as but not limited to Mn-doped ZnS, CdS, and CdSe quantum dots (QD), which, to the best of our knowledge, denote promising candidates for a variety of optoelectronic applications. Specifically, we have carefully optimized the synthesis conditions in order to generate a series of chemically well-defined Mn-doped Zn 2SiO 4 not only possessing Mn concentrations ranging from 3% to 8% but also characterized by highly crystalline, monodisperse wire-like motifs measuring ~30 nm in diameter and ~700 nm in length. Optically, the photoluminescence signals associated with the 1D series yielded a volcano-shaped relationship between PL intensities and the Mn dopant level. In additional experiments, we have immobilized CdSe quantum dots (QDs) onto the external surfaces of our as-synthesized Mn-doped Zn 2SiO 4 nanowires, in order to form novel composite heterostructures. The optical properties of the CdSe QD–Mn:Zn 2SiO 4 heterostructures have been subsequently examined. Our results have demonstrated the likely co-existence of both energy transfer and charge transfer phenomena between the two constituent components of our as-prepared composites. Specifically, when both components are photoexcited, both energy transfer and charge transfer were found to plausibly occur, albeit in opposite directions. When the CdSe QDs are excited alone for example, charge transfer probably takes place from the CdSe QDs to the dopant Mn 2+ ions. We believe that our as-processed heterostructures are therefore promising as a tunable light-harvesting motif. Essentially, these materials have broadened the effective light absorption range for optical ‘accessibility’, not only through their incorporation of dopant-tunable Zn 2SiO 4 possessing complementary absorption properties to those of the QDs but also through their integration of CdSe QDs with size-tailorable optical behavior.« less

Synthesis, properties, and formation mechanism of Mn-doped Zn 2 SiO 4 nanowires and associated heterostructures

DOE PAGES

Liu, Haiqing; Moronta, Dominic; Li, Luyao; ...

2018-03-28

In this study, we have put forth a facile hydrothermal approach to synthesize an array of one-dimensional (1D) Mn-doped Zn 2SiO 4 nanostructures. Specifically, we have probed and correlated the effects of controllable reaction parameters such as the pH and Mn dopant concentrations with the resulting crystal structures and morphologies of the products obtained. Based upon our results, we find that careful tuning of the pH versus the Mn dopant level gives rise to opposite trends with respect to the overall size of the resulting one-dimensional nanostructures. Significantly, we have highlighted the role of the Mn dopant ion concentration asmore » a potentially generalizable reaction parameter in solution-based synthesis for controlling morphology and hence, the observed optical behavior. Indeed, such a strategy can be potentially generalized to systems such as but not limited to Mn-doped ZnS, CdS, and CdSe quantum dots (QD), which, to the best of our knowledge, denote promising candidates for a variety of optoelectronic applications. Specifically, we have carefully optimized the synthesis conditions in order to generate a series of chemically well-defined Mn-doped Zn 2SiO 4 not only possessing Mn concentrations ranging from 3% to 8% but also characterized by highly crystalline, monodisperse wire-like motifs measuring ~30 nm in diameter and ~700 nm in length. Optically, the photoluminescence signals associated with the 1D series yielded a volcano-shaped relationship between PL intensities and the Mn dopant level. In additional experiments, we have immobilized CdSe quantum dots (QDs) onto the external surfaces of our as-synthesized Mn-doped Zn 2SiO 4 nanowires, in order to form novel composite heterostructures. The optical properties of the CdSe QD–Mn:Zn 2SiO 4 heterostructures have been subsequently examined. Our results have demonstrated the likely co-existence of both energy transfer and charge transfer phenomena between the two constituent components of our as-prepared composites. Specifically, when both components are photoexcited, both energy transfer and charge transfer were found to plausibly occur, albeit in opposite directions. When the CdSe QDs are excited alone for example, charge transfer probably takes place from the CdSe QDs to the dopant Mn 2+ ions. We believe that our as-processed heterostructures are therefore promising as a tunable light-harvesting motif. Essentially, these materials have broadened the effective light absorption range for optical ‘accessibility’, not only through their incorporation of dopant-tunable Zn 2SiO 4 possessing complementary absorption properties to those of the QDs but also through their integration of CdSe QDs with size-tailorable optical behavior.« less

Interplay of local structure, charge, and spin in bilayered manganese perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. In this paper, we show results of high-energy resolution x-ray absorption and emission spectroscopies on amore » $${\\mathrm{La}}_{2{-}2x}{\\mathrm{Sr}}_{1+2x}{\\mathrm{Mn}}_{2}{\\mathrm{O}}_{7}$$ family of bilayered manganites in a broad doping range $$(0.5{\\le}x{\\le}1)$$. We established a relation between local Mn charge and Mn-O distances as a function of doping. Finally, based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.« less

Interplay of local structure, charge, and spin in bilayered manganese perovskites

DOE PAGES

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz; ...

2018-03-27

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. In this paper, we show results of high-energy resolution x-ray absorption and emission spectroscopies on amore » $${\\mathrm{La}}_{2{-}2x}{\\mathrm{Sr}}_{1+2x}{\\mathrm{Mn}}_{2}{\\mathrm{O}}_{7}$$ family of bilayered manganites in a broad doping range $$(0.5{\\le}x{\\le}1)$$. We established a relation between local Mn charge and Mn-O distances as a function of doping. Finally, based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.« less

Methanol adsorption and dissociation on LaMnO 3 and Sr doped LaMnO 3 (001) surfaces

DOE PAGES

Beste, Ariana

2017-06-20

Using density functional theory, we investigate in this paper methanol adsorption and dissociation on the MnO 2- and LaO-terminated LaMnO 3 (001) surface as a function of Sr dopant enrichment in and near the surface. In response to bulk cleavage, we find electron depletion of the negatively charged MnO 2 surface layer that is enhanced by Sr doping in the subsurface. In contrast, we observe electron accumulation in the positively charged LaO surface layer that is reduced by Sr doping in the surface layer. Methanol adsorbs dissociatively on the LaO termination of the LaMnO 3 (001) surface. Methanol adsorption onmore » the LaO termination is strongly preferred over adsorption on the MnO 2 termination. While moderate doping has a small influence on methanol adsorption and dissociation, when 100% of La is replaced by Sr in the surface or subsurface, the adsorption preference of methanol is reversed. Finally, if the surface is highly dopant enriched, methanol favours dissociative adsorption on the MnO 2-terminated surface.« less

Methanol adsorption and dissociation on LaMnO 3 and Sr doped LaMnO 3 (001) surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beste, Ariana

Using density functional theory, we investigate in this paper methanol adsorption and dissociation on the MnO 2- and LaO-terminated LaMnO 3 (001) surface as a function of Sr dopant enrichment in and near the surface. In response to bulk cleavage, we find electron depletion of the negatively charged MnO 2 surface layer that is enhanced by Sr doping in the subsurface. In contrast, we observe electron accumulation in the positively charged LaO surface layer that is reduced by Sr doping in the surface layer. Methanol adsorbs dissociatively on the LaO termination of the LaMnO 3 (001) surface. Methanol adsorption onmore » the LaO termination is strongly preferred over adsorption on the MnO 2 termination. While moderate doping has a small influence on methanol adsorption and dissociation, when 100% of La is replaced by Sr in the surface or subsurface, the adsorption preference of methanol is reversed. Finally, if the surface is highly dopant enriched, methanol favours dissociative adsorption on the MnO 2-terminated surface.« less

TL and OSL properties of Mn2+-doped MgGa2O4 phosphor

NASA Astrophysics Data System (ADS)

Luchechko, A.; Zhydachevskyy, Ya; Maraba, D.; Bulur, E.; Ubizskii, S.; Kravets, O.

2018-04-01

The oxide MgGa2O4 spinel ceramics doped with Mn2+ ions was synthesized by a solid-state reaction at 1200 °C in air. The activator concentration was equal 0.05 mol% of MnO. Phase purity of the synthesized samples was analyzed by X-ray diffraction technique. This spinel ceramics show efficient green emission in the range from 470 to 550 nm with a maximum at about 505 nm under UV or X-ray excitations, which is due to Mn2+ ions. MgGa2O4: Mn2+ exhibits intense thermoluminescence (TL) and optically stimulated luminescence (OSL) after influence of ionizing radiation. Are complex nature of the TL glow curves is associated with a significant number of structural defects that are responsible for the formation of shallow and deep electron traps. In this work, time-resolved OSL characteristics of the samples exposed to beta particles are reported for the first time. A light from green LED was used for optical stimulation. Obtained TL and OSL results suggest MgGa2O4:Mn2+ as perspective material for further research and possible application in radiation dosimetry.

Magnetic impurity effect on charge and magnetic order in doped La1.5Ca0.5CoO4

NASA Astrophysics Data System (ADS)

Horigane, K.; Hiraka, H.; Tomiyasu, K.; Ohoyama, K.; Louca, D.; Yamada, K.

2012-02-01

Neutron scattering experiments were performed on single crystals of magnetic impurity doped cobalt oxides La1.5Ca0.5CoO4 to characterize the charge and spin orders. We newly found contrasting impurity effects. Two types of magnetic peaks are observed at q = (0.5,0,L) with L = half-integer and integer in La1.5Ca0.5CoO4, while magnetic peak at L = half-integer (integer) was only observed in Mn (Fe)-substituted sample. Although Mn and Fe impurities degrade charge and magnetic order, Cr impurity stabilizes the ordering at x = 0.5. Based on the crystal structural analysis of Cr doped sample, we found that the excess oxygen and change of octahedron around Co3+ were realized in Cr doped sample.

Manganese-induced magnetic symmetry breaking and its correlation with the metal-insulator transition in bilayered S r3(Ru1-xM nx) 2O7

NASA Astrophysics Data System (ADS)

Zhang, Qiang; Ye, Feng; Tian, Wei; Cao, Huibo; Chi, Songxue; Hu, Biao; Diao, Zhenyu; Tennant, David A.; Jin, Rongying; Zhang, Jiandi; Plummer, Ward

2017-06-01

Bilayered S r3R u2O7 is an unusual metamagnetic metal with inherently antiferromagnetic (AFM) and ferromagnetic (FM) fluctuations. Partial substitution of Ru by Mn results in the establishment of a metal-insulator transition (MIT) at TMIT and AFM ordering at TM in S r3(Ru1-xM nx) 2O7 . Using elastic neutron scattering, we investigated the effect of Mn doping on the magnetic structure, in-plane magnetic correlation lengths and their correlation to the MIT in S r3(Ru1-xM nx) 2O7 (x =0.06 and 0.12). With the increase of Mn doping (x ) from 0.06 to 0.12 or the decrease of temperatures for x =0.12 , an evolution from an in-plane short-range to long-range antiferromagnetic (AFM) ground state occurs. For both compounds, the magnetic ordering has a double-stripe configuration, and the onset of magnetic correlation with an anisotropic behavior coincides with the sharp rise in electrical resistivity and specific heat. Since it does not induce a measurable lattice distortion, the double-stripe antiferromagnetic order with anisotropic spin texture breaks symmetry from a C4 v crystal lattice to a C2 v magnetic sublattice. These observations shed light on an age-old question regarding the Slater versus Mott-type MIT.

Flux-pinning and inhomogeneity in MgB 2 /Fe wires

NASA Astrophysics Data System (ADS)

Husnjak, O.; Babić, E.; Kušević, I.; Wang, X. L.; Soltanian, S.; Dou, S. X.

2007-08-01

Transport critical current densities Jc and irreversibility fields B of undoped and nanoparticle doped (10 wt% SiC) Fe-sheathed MgB 2 wires were measured from 2 to 40 K in magnetic field B≤16 T. For the best segments of wires (≤1 cm) both the magnitude and field variations of Jc and the pinning force density Fp=JcB depend only on the magnitude of B, hence the strength of flux-pinning. B of doped wire for T≤30 K is ˜1.4 times larger than that of undoped and reaches that of NbTi (10 T at 4.2 K) already at 20 K. Accordingly, its high-field Jcs and Fps are large, typically three times larger than the best literature results, and are limited by the porosity and inhomogeneity of the superconducting cores in present-day MgB 2 wires.

Magnetic properties and photovoltaic applications of ZnO:Mn nanocrystals.

PubMed

Zhang, Ying; Han, Fengxiang; Dai, Qilin; Tang, Jinke

2018-05-01

A simple and large-scale synthetic method of Mn doped ZnO (ZnO:Mn) was developed in this work. ZnO:Mn nanocrystals with hexagonal structure were prepared by thermal decomposition of zinc acetate and manganese acetate in the presence of oleylamine and oleic acid with different temperatures, ligand ratios, and Mn doping concentrations. The particle size (47-375 nm) and morphology (hexagonal nanopyramid, hexagonal nanodisk and irregular nanospheres) of ZnO:Mn nanocrystals can be controlled by the ratio of capping ligand, reaction temperature, reaction time and Mn doping concentration. The corresponding optical and magnetic properties were systemically studied and compared. All samples were found to be paramagnetic with antiferromagnetic (AFM) exchange interactions between the Mn moments in the ZnO lattice, which can be affected by the reaction conditions. The quantum dot sensitized solar cells (QDSSCs) were fabricated based on ZnO:Mn nanocrystals and CdS quantum dots, and the device performance affected by Mn doping concentration was also studied and compared. Copyright © 2018 Elsevier Inc. All rights reserved.

Robustness of magnetic and electric domains against charge carrier doping in multiferroic hexagonal ErMnO 3

DOE PAGES

Hassanpour, E.; Wegmayr, V.; Schaab, J.; ...

2016-04-12

We investigate the effect of chemical doping on the electric and magnetic domain pattern in multiferroic hexagonal ErMnO 3 . Hole- and electron doping are achieved through the growth of Er 1-x Ca x MnO 3 and Er 1-x Zr x MnO 3 single crystals, which allows for a controlled introduction of divalent and tetravalent ions, respectively. Using conductance measurements, piezoresponse force microscopy and nonlinear optics we study doping-related variations in the electronic transport and image the corrsponding ferroelectric and antiferromagnetic domains. We find that moderate doping levels allow for adjusting the electronic conduction properties of ErMnO 3 without destroyingmore » its characteristic domain patterns. Our findings demonstrate the feasibility of chemical doping for nonperturbative property-engineering of intrinsic domain states in this important class of multiferroics.« less

Photoluminescence and cathodoluminescence of Mn doped zinc silicate nanophosphors for green and yellow field emissions displays

NASA Astrophysics Data System (ADS)

Omri, K.; Alyamani, A.; Mir, L. El

2018-02-01

Mn2+-doped Zn2SiO4 (ZSM2+) was synthesized by a facile sol-gel technique. The obtained samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, photoluminescence (PL) and cathodoluminescence (CL) techniques. Under UV excitation, spectra showed that the α-ZSM2+ phosphor exhibited a strong green emission around 525 nm and reached the highest luminescence intensity with the Mn doping concentration of 5 at.%. However, for the β-ZSM2+ phase, an interesting yellow emission band centered at 575 nm of Mn2+ at the Zn2+ tetrahedral sites was observed. In addition, an unusual red shift with increasing Mn2+ content was also found and attributed to an exchange interaction between Mn2+. Both PL and CL spectra exhibit an intense green and yellow emission centered at 525 and 573 nm, respectively, due to the 4T1 (4G)-6A1 (6S) transition of Mn2+. Furthermore, these results indicated that the Mn2+-doped zinc silicate phosphors may have potential applications in green and yellow emissions displays like field emission displays (FEDs).

Electronic self-organization in the single-layer manganite $$\\rm Pr_{1-x}Ca_{1+x}MnO4$$

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Feng; Chi, Songxue; Fernandez-Baca, Jaime A

We use neutron scattering to investigate the doping evolution of the magnetic correlations in the single-layer manganitemore » $$\\rm Pr_{\\it 1-x}Ca_{\\it 1+x}MnO_4$$, away from the $x=0.5$ composition where the CE-type commensurate antiferromagnetic (AF) structure is stable. We find that short-range incommensurate spin correlations develop as the system is electron doped ($x<0.5$), which coexist with the CE-type AF order. This suggests that electron doping in this system induces an inhomogeneous electronic self-organization, where commensurate AF patches with $x=0.5$ are separated by electron-rich domain walls with short range magnetic correlations. This behavior is strikingly different than for the three-dimensional $$\\rm Pr_{\\it 1-x}Ca_{\\it x}MnO_3$$, where the long-range CE-type commensurate AF structure is stable over a wide range of electron or hole doping around $x=0.5$.« less

In vitro study of manganese-doped bioactive glasses for bone regeneration.

PubMed

Miola, Marta; Brovarone, Chiara Vitale; Maina, Giovanni; Rossi, Federica; Bergandi, Loredana; Ghigo, Dario; Saracino, Silvia; Maggiora, Marina; Canuto, Rosa Angela; Muzio, Giuliana; Vernè, Enrica

2014-05-01

A glass belonging to the system SiO2-P2O5-CaO-MgO-Na2O-K2O was modified by introducing two different amounts of manganese oxide (MnO). Mn-doped glasses were prepared by melt and quenching technique and characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) observation and energy dispersion spectrometry (EDS) analysis. In vitro bioactivity test in simulated body fluid (SBF) showed a slight decrease in the reactivity kinetics of Mn-doped glasses compared to the glass used as control; however the glasses maintained a good degree of bioactivity. Mn-leaching test in SBF and minimum essential medium (MEM) revealed fluctuating trends probably due to a re-precipitation of Mn compounds during the bioactivity process. Cellular tests showed that all the Mn-doped glasses, up to a concentration of 50 μg/cm(2) (μg of glass powders/cm(2) of cell monolayer), did not produce cytotoxic effects on human MG-63 osteoblasts cultured for up to 5 days. Finally, biocompatibility tests demonstrated a good osteoblast proliferation and spreading on Mn-doped glasses and most of all that the Mn-doping can promote the expression of alkaline phosphatase (ALP) and some bone morphogenetic proteins (BMPs). Copyright © 2014 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahamdioua, N., E-mail: mahamdioua.nabil@gmail.com; Amira, A.; Altintas, S.P.

We present structural, magnetic and electrical properties of the polycrystalline A-site-deficient yttrium doped double layered manganites La{sub 1.2−x}□{sub 0.2}Y{sub x}Ca{sub 1.6}Mn{sub 2}O{sub 7} (x=0.2, 0.3 and 0.4) prepared by a solid state reaction method. The samples crystallize in the tetragonal structure with the space group I4/mmm. Doping with Y decreases the cell parameters and causes a decrease of the metal-insulator transition temperature. The same evolution with doping is also seen for the deduced Curie temperature from susceptibility curves which present a clear paramagnetic-ferromagnetic transition. The significant positive intrinsic magnetoresistance, shown in all samples, reaches 85% at 122 K under 7more » T for 0.3 doped sample and can be attributed to the suppression of spin fluctuations via aligning the spins under external magnetic field, while the extrinsic one is attributed to the inter-grain spin-polarized tunneling across the grain boundaries. The simulation of the resistivity curves in the entire temperature range show that the percolation model is suitable to fit our results. The applied magnetic field increases the density of states near the Fermi level, which is in accordance with the observed decrease of resistivity. - Graphical abstract: Resistivity and magnetoresistance of La{sub 1.2−x}□{sub 0.2}Y{sub x}Ca{sub 1.6}Mn{sub 2}O{sub 7} (x=0.2, 0.3, 0.4). Solid lines correspond to the fitting results. Display Omitted.« less

The Intrinsic Ferromagnetism in a MnO2 Monolayer.

PubMed

Kan, M; Zhou, J; Sun, Q; Kawazoe, Y; Jena, P

2013-10-17

The Mn atom, because of its special electronic configuration of 3d(5)4s(2), has been widely used as a dopant in various two-dimensional (2D) monolayers such as graphene, BN, silicene and transition metal dichalcogenides (TMDs). The distributions of doped Mn atoms in these systems are highly sensitive to the synthesis process and conditions, thus suffering from problems of low solubility and surface clustering. Here we show for the first time that the MnO2 monolayer, synthetized 10 years ago, where Mn ions are individually held at specific sites, exhibits intrinsic ferromagnetism with a Curie temperature of 140 K, comparable to the highest TC value achieved experimentally for Mn-doped GaAs. The well-defined atomic configuration and the intrinsic ferromagnetism of the MnO2 monolayer suggest that it is superior to other magnetic monolayer materials.

Hybrid density functional study of structural, bonding, and electronic properties of the manganite series La1-xCaxMnO3 (x =0,1/4,1)

NASA Astrophysics Data System (ADS)

Korotana, R.; Mallia, G.; Gercsi, Z.; Liborio, L.; Harrison, N. M.

2014-05-01

Hybrid-exchange density functional theory calculations are carried out to determine the effects of A-site doping on the electronic and magnetic properties of the manganite series La1-xCaxMnO3. This study focuses on the ground state of an ordered Ca occupancy in a periodic structure. It is shown that the hybrid-exchange functional, Becke three-parameter Lee-Yang-Parr (B3LYP), provides an accurate and consistent description of the electronic structure for LaMnO3, CaMnO3, and La0.75Ca0.25MnO3. We have quantified the relevant structural, magnetic, and electronic energy contributions to the stability of the doped compound. An insight into the exchange coupling mechanism for the low hole density region of the phase diagram, where a polaron (anti-Jahn-Teller) forms, is also provided. This study completes a microscopic description of the lightly doped insulator with an antiferromagnetic-to-ferromagnetic and metal-to-insulator transition.

Enhanced strain effect of aged acceptor-doped BaTiO3 ceramics with clamping domain structures

NASA Astrophysics Data System (ADS)

Wang, Lei; Zhou, Zhiyong; Zhao, Xiaobo; Liu, Zhen; Liang, Ruihong; Dong, Xianlin

2017-03-01

A clamping domain structure is proposed to improve the amount of non-180° domain switching in BaTiO3 based piezoelectric ceramics. Experimental results show a large unipolar strain of 0.23% at 5 kV/mm in aged 0.5 mol. % Mn doped BaTiO3 ceramics with clamping domain structures, and the normalized strain (d33*= Smax/Emax) reaches 600 pm/V at low electric fields of 2 or 3 kV/mm. In contrast, pure BaTiO3 ceramics with clamping domain structures exhibit no clear polarization constriction or strain enhancement at 3 kV/mm. Electron paramagnetic resonance spectra verify the existence of titanium vacancies, Mn2+ and Mn4+, in 0.5 mol. % Mn doped BaTiO3 ceramics. These results indicate that the enhanced strain effect can be attributed to the combined effect of the clamping domain structure and stabilization of defect dipoles. This method provides a general way to obtain large strain in ferroelectrics.

Polycrystalline ZnO and Mn-doped ZnO nanorod arrays with variable dopant content via a template based synthesis from Zn(II) and Mn(II) Schiff base type single source molecular precursors

NASA Astrophysics Data System (ADS)

Pashchanka, Mikhail; Hoffmann, Rudolf C.; Burghaus, Olaf; Corzilius, Björn; Cherkashinin, Gennady; Schneider, Jörg J.

2011-01-01

The synthesis and full characterisation of pure and Mn-doped polycrystalline zinc oxide nanorods with tailored dopant content are obtained via a single source molecular precursor approach using two Schiff base type coordination compounds is reported. The infiltration of precursor solutions into the cylindrical pores of a polycarbonate template and their thermal conversion into a ceramic green body followed by dissolution of the template gives the desired ZnO and Mn-doped ZnO nanomaterial as compact rods. The ZnO nanorods have a mean diameter between 170 and 180 nm or 60-70 nm, depending on the template pore size employed, comprising a length of 5-6 μm. These nanorods are composed of individual sub-5 nm ZnO nanocrystals. Exact doping of these hierarchically structured ZnO nanorods was achieved by introducing Mn(II) into the ZnO host lattice with the precursor complex Diaquo-bis[2-(meth-oxyimino)-propanoato]manganese, which allows to tailor the exact Mn(II) doping content of the ZnO rods. Investigation of the Mn-doped ZnO samples by XRD, TEM, XPS, PL and EPR, reveals that manganese occurs exclusively in its oxidation state + II and is distributed within the volume as well as on the surface of the ZnO host.

First-principles study of Mn-S codoped anatase TiO2

NASA Astrophysics Data System (ADS)

Li, Senlin; Huang, Jinliang; Ning, Xiangmei; Chen, Yongcha; Shi, Qingkui

2018-04-01

In this work, the CASTEP program in Materials Studio 2017 software package was applied to calculate the electronic structures and optical properties of pure anatase TiO2, S-doped, Mn-doped and Mn-S co-doped anatase TiO2 by GGA + U methods based on the density function theory (DFT). The results indicate that the lattice is distorted and the lattice constant is reduce due to doping. The doping also introduces impurity energy levels into the forbidden band. After substitution of Mn for Ti atom, band gap narrowing of anatase TiO2 is caused by the impurity energy levels appearance in the near Fermi surface, which are contributed by Mn-3d orbital, Ti-3d orbital and O-2p orbital hybridization. After substitution of S for O atom, band gap narrowing is creited with the shallow accepter level under the conduction hand of S-3p orbital. The Mn-S co-doped anatase TiO2 could be a potential candidate for a photocatalyst because of tis enhanced absorption ability of visible light. The results can well explain the immanent cause of a band gap narrowing as well as a red shift in the spectrum for doped anatase TiO2.

Patterning of silver nanoparticles on visible light-sensitive Mn-doped lithium niobate photogalvanic crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Xiaoyan; Ohuchi, Fumio; Hatano, Hideki

2011-08-01

Visible light-induced polarization-dependent photochemical deposition of silver nanoparticles (AgNPs) has been demonstrated using Mn-doped congruent LiNbO{sub 3} (CLN) single crystals. Mn-doped CLN has a strong absorption over a wide region of the visible spectrum that allowed effective visible light irradiation for photochemical deposition. The AgNPs deposition on Mn-doped CLN was compared with that on non-doped congruent LiNbO{sub 3}, and together these further confirmed that the photochemical deposition on LiNbO{sub 3} is caused by the strong photogalvanic effect.

Photoluminescence properties of Mn2+/Yb3+ co-doped oxyfluoride glasses for solar cells application

NASA Astrophysics Data System (ADS)

Yan, Ying; Chen, Zeng; Jia, Xiyang; Li, Shengjun

2018-01-01

Mn2+/Yb3+ co-doped oxyfluoride glasses were facilely synthesized in the SiO2-Al2O3-Na2O-CaF2 system. Partial crystallization processed during the preparation of the glasses, by which small amounts of CaF2 nano-crystals were formed. Under ultraviolet and blue (370-500 nm) light excitation, an efficient down-conversion involving the emission of near-infrared is realized in the Mn2+/Yb3+ co-doped oxyfluoride glasses. The near-infrared emission peaks mainly at 976 nm and secondarily at 1020 nm, which is a comfortable match with the band gap of c-Si. The variation in visible and near-infrared spectra and the decay curves of Mn2+:4T1 → 6A1 emission have been investigated to verify the possible energy transfer from Mn2+ ions to Yb3+ ions. On analyzing the energy transfer processes theoretically and experimentally, we propose that quantum cutting and down-shifting processes may occur simultaneously in the samples. We suggest that the Mn2+-Yb3+ co-doped materials can provide a novel direction to realize UV-Vis to NIR down-conversion for Si solar cells.

Mn-doped quantum dot sensitized solar cells: a strategy to boost efficiency over 5%.

PubMed

Santra, Pralay K; Kamat, Prashant V

2012-02-08

To make Quantum Dot Sensitized Solar Cells (QDSC) competitive, it is necessary to achieve power conversion efficiencies comparable to other emerging solar cell technologies. By employing Mn(2+) doping of CdS, we have now succeeded in significantly improving QDSC performance. QDSC constructed with Mn-doped-CdS/CdSe deposited on mesoscopic TiO(2) film as photoanode, Cu(2)S/Graphene Oxide composite electrode, and sulfide/polysulfide electrolyte deliver power conversion efficiency of 5.4%.

Tuning of magnetism in DyMn1-xFexO3 (x<0.1) system by iron substitution

NASA Astrophysics Data System (ADS)

Mihalik, Matúš; Mihalik, Marián; Zentková, Mária; Uhlířová, Klára; Kratochvílová, Marie; Fitta, Magdalena; Quintero, Pedro A.; Meisel, Mark W.

2018-05-01

The effect of Fe doping on the magnetism of DyMn1-xFexO3 (x<0.1) single crystals is reported. Specifically, TN of the Mn sublattice decreases from 38 K (x = 0) to 33 K (x = 0.1), TS = 17.9 K (x = 0) connected with the transition of Mn-spins into the cycloidal magnetic phase decreases to 15.9 K (x = 0.01) and vanishes for higher x concentrations, while the ordering temperature of the Dy sublattice varies between 5.9 K (x = 0.01) and 4.1 K (x = 0.02). These results indicate the ground state magnetic structure of DyMnO3 can be destabilized, and the multiferroicity is completely suppressed by very low Fe doping. Similar effects were previously observed in the multiferroic TbMn1-xFexO3 system.

Morphology-controlled synthesis and novel microwave electromagnetic properties of hollow urchin-like chain Fe-doped MnO 2 under 10 T high magnetic field

NASA Astrophysics Data System (ADS)

Yuping, Duan; Jia, Zhang; Hui, Jing; Shunhua, Liu

2011-05-01

Fe-doped MnO 2 with a hollow sea urchin-like ball chain shape was first synthesized under a high magnetic field of 10 T. The formation mechanism was investigated and discussed in detail. The synthesized samples were characterized by XRD, SEM, TEM, EMPA, and vector network analysis. By doping MnO 2 with Fe, the relative complex permittivity of MnO 2 and its corresponding loss tangent clearly decreases, but its relative complex permeability and its corresponding loss tangent markedly increases. Moreover, the theoretically calculated values of reflection loss show that with increasing the Fe content, the as-prepared Fe-doped MnO 2 exhibits good microwave absorption capability.

Effect of field cooling heights on the levitation force of pure and starch/polystyrene/MWCNT added bulk MgB2 superconductors

NASA Astrophysics Data System (ADS)

Tripathi, D.; Dey, T. K.

2014-12-01

A series of MgB2 pellets with and without addition of carbon from different sources (viz. starch, polystyrene and carbon nanotubes) have been synthesized by solid state reaction under argon atmosphere. XRD analysis indicates a decrease in lattice parameters of MgB2 with addition of starch, polystyrene (PS) and MWCNT and confirms substitution of carbon in boron sites. The presence of nanosized carbon inclusions between the grain boundaries in the present set of samples is evident in TEM photographs. Resistivity data confirms a decrease in superconducting transition temperature (Tc0) for MgB2 doped with starch/PS/MWCNT. The effect of different field cooling heights (HIFC) at 20 K on maximum levitation force (FMLF) and maximum attractive force (FMAF) of pure MgB2 and MgB2 doped with starch/PS/MWCNT have been investigated. Except for MWCNT, doping of starch and PS in MgB2 is found to improve FMLF and FMAF and the best result is obtained for MgB2 doped with 1 wt.% PS. Levitation force measured as a function of decreasing initial field cooling height indicates exponential dependence of both maximum levitation force (FMLF) and maximum attractive force (FMAF). However, the gap distance between PM and the sample (H0AF and HMAF) corresponding to maximum attractive force (FMAF) and zero attractive force (F0AF) varies linearly and their difference remains constant. This constancy in (HMAF - H0AF) is understood in terms of constant reduction rate of magnetic flux density between H0AF and HMAF.

Difference between resistance degradation of fixed valence acceptor (Mg) and variable valence acceptor (Mn)-doped BaTiO3 ceramics

NASA Astrophysics Data System (ADS)

Yoon, Seok-Hyun; Randall, Clive A.; Hur, Kang-Heon

2010-09-01

The difference in the resistance degradation behavior was investigated between fixed valence acceptor (Mg) and the variable valence acceptor (Mn)-doped BaTiO3 ceramics with an increase of each acceptor concentration. Coarse-grained specimens with uniform grain sizes and different acceptor concentrations were prepared. In the case of Mg-doped BaTiO3, the time to degradation systematically decreased with the increase in Mg concentration. In contrast, there is a systematically increased time to degradation with the increase in Mn concentration in Mn-doped BaTiO3. The fast degradation by the increase in Mg concentration directly corresponded to an increase in the Warburg impedance and ionic transference number (tion) associated with an increase in oxygen vacancy concentration ([VO••]). On the other hand, no distinct Warburg impedance or ionic conduction contribution could be observed with the increase in Mn concentration. It is supposed that the increase in [VO••] is negligible in spite of the increase in acceptor Mn concentration, when it is compared to Mg-doped BaTiO3. The much lower [VO••] and more dominant electron/hole trapping effect due to multivalence nature of Mn are supposed to cause such a contrary degradation behavior between Mg and Mn-doped BaTiO3. Reoxidation in a slightly reducing atmosphere (N2) showed better resistance to degradation behavior than in a oxidizing air atmosphere in both Mg and Mn-doped BaTiO3, which is anticipated to be an increase in the electron/hole trapping sites. All these behaviors could be explained by the low temperature defect chemical model that shows difference in the defect structure between Mg and Mn-doped BaTiO3, and its dependence on the oxygen partial pressure (pO2) during reoxidation and cooling. Not only the [VO••], but also the density of electron/hole trap sites, are believed to be crucial in controlling resistance degradation.

Antiferromagnetic instability in Sr3Ru2O7: stabilized and revealed by dilute Mn impurities

NASA Astrophysics Data System (ADS)

Hossain, Muhammed; Bohnenbuck, B.; Chuang, Y.-D.; Cruz, E.; Wu, H.-H.; Tjeng, L. H.; Elfimov, I. S.; Hussain, Z.; Keimer, B.; Sawatzky, G. A.; Damascelli, A.

2009-03-01

X-ray Absorption Spectroscopy (XAS) and Resonant Elastic Soft X-ray Scattering (RESXS) studies have been performed on Mn-doped Sr3Ru2O7, both on the Ru and Mn L-edges, to investigate the origin of the metal insulator transition. Extensive simulations based on our experimental findings point toward an intrinsic antiferromagnetic instability in the parent Sr3Ru2O7 compound that is stabilized by the dilute Mn impurities. We show that the metal-insulator transition is a direct consequence of the antiferromagnetic order and we propose a phenomenological model that may be applicable also to metal-insulator transitions seen in other oxides. Moreover, a comparison of Ru and Mn L-edge data on 5% Mn doped system reveals that dilute Mn impurities are generating much more intense signal than Ru which is occupying 95% of the lattice sites. This suggests the embedding of dilute impurities as a powerful mean to probe weak and, possibly, spatially inhomogeneous order in solid-state systems. In collaboration with: Y. Yoshida (AIST), J. Geck, D.G. Hawthorn (UBC), M.W. Haverkort, Z. Hu, C. Sch"ußler-Langeheine (Cologne), R. Mathieu, Y. Tokura, S. Satow, H. Takagi (Tokyo), J.D. Denlinger (ALS).

Galvanostatically deposited Fe: MnO2 electrodes for supercapacitor application

NASA Astrophysics Data System (ADS)

Dubal, D. P.; Kim, W. B.; Lokhande, C. D.

2012-01-01

The present investigation describes the addition of iron (Fe) in order to improve the supercapacitive properties of MnO2 electrodes using galvanostatic mode. These amorphous worm like Fe: MnO2 electrodes are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR) and wettability test. The supercapacitive properties of MnO2 and Fe: MnO2 electrodes are investigated using cyclic voltammetry, chronopotentiometry and impedance techniques. It is seen that the supercapacitance increases with increase in Fe doping concentration and achieved a maximum of 173 F g-1 at 2 at% Fe doping. The maximum supercapacitance obtained is 218 F g-1 for 2 at% Fe: MnO2 electrode. This hydrous binary oxide exhibited ideal capacitive behavior with high reversibility and high pulse charge-discharge property between -0.1 and +0.9 V/SCE in 1 M Na2SO4 electrolyte indicating a promising electrode material for electrochemical supercapacitors.

Effects of transition-metal ions on the morphology and electrochemical properties of δ-MnO2 for supercapacitors

NASA Astrophysics Data System (ADS)

Wang, Jia-Wei; Chen, Ya; Chen, Bai-Zhen

2014-11-01

δ-MnO2 materials doped with transition-metal cations (Zn, Co, and Ag) were successfully synthesized using a hydrothermal technique. The structures and morphologies of the obtained oxides were analyzed using X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller measurements. Additionally, the electrochemical properties were evaluated through cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic cycling measurements. The results indicate that the pure and doped samples crystallize in the δ form with a layered structure and that the Mn/Zn, Mn/Co and Mn/Ag molar ratios are all approximately 1:0.09. Both the Zn-doped and pure MnO2 materials exhibit a petal-like morphology; however, the former has a higher specific surface area of up to 98.97m2 g-1. Furthermore, the Zn-doped MnO2 exhibits a near-rectangular cyclic voltammetry (CV) curve with broad quasi-reversible redox peaks and a specific capacitance of 182.9 F g-1 at a CV scan rate of 2 mV s-1. The Co-doped material exhibits a distinct spiny-fiber morphology, and the electrochemical performance of this material is significantly worse than that of pure MnO2. The average attenuation rate of the Ag-doped material is only 0.028% after 1000 cycles, which is lower than that of pure MnO2.

Effect of A-site deficiency in LaMn{sub 0.9}Co{sub 0.1}O{sub 3} perovskites on their catalytic performance for soot combustion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dinamarca, Robinson; Garcia, Ximena; Jimenez, Romel

Highlights: • A-site defective perovskites increases the oxidation state of the B-cation. • Not always non-stoichiometric perovskites exhibit higher catalytic activity in soot combustion. • The highly symmetric cubic crystalline structure diminishes the redox properties of perovskites. - Abstract: The influence of lanthanum stoichiometry in Ag-doped (La{sub 1-x}Ag{sub x}Mn{sub 0.9}Co{sub 0.1}O{sub 3}) and A-site deficient (La{sub 1-x}Mn{sub 0.9}Co{sub 0.1}O{sub 3-δ}) perovskites with x equal to 10, 20 and 30 at.% has been investigated in catalysts for soot combustion. The catalysts were prepared by the amorphous citrate method and characterized by XRD, nitrogen adsorption, XPS, O{sub 2}-TPD and TPR. The formationmore » of a rhombohedral excess-oxygen perovskite for Ag-doped and a cubic perovskite structure for an A-site deficient series is confirmed. The efficient catalytic performance of the larger Ag-doped perovskite structure is attributed to the rhombohedral crystalline structure, Ag{sub 2}O segregated phases and the redox pair Mn{sup 4+}/Mn{sup 3+}. A poor catalytic activity for soot combustion was observed with A-site deficient perovskites, despite the increase in the redox pair Mn{sup 4+}/Mn{sup 3+}, which is attributed to the cubic crystalline structure.« less

Intrinsic ferromagnetism in nanocrystalline Mn-doped ZnO depending on Mn concentration.

PubMed

Subramanian, Munisamy; Tanemura, Masaki; Hihara, Takehiko; Soga, Tetsuo; Jimbo, Takashi

2011-04-01

The physical properties of Zn(1-x)Mn(x)O nanoparticles synthesized by thermal decomposition are extensively investigated by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman light scattering and Hysteresis measurements. XRD and XPS spectra reveal the absence of secondary phase in nanocrystalline ZnO doped with 5% or less Mn; and, later confirms that the valance state of Mn to be 2+ for all the samples. Raman spectra exhibit a peak at 660 cm(-1) which we attribute to the intrinsic lattice defects of ZnO with increasing Mn concentration. Overall, our results demonstrate that ferromagnetic properties can be realized while Mn-doped ZnO obtained in the nanocrystalline form.

Synthesis, structural, optical and dielectric properties of transition metal doped ZnMnO nanoparticles by sol-gel combustion technique

NASA Astrophysics Data System (ADS)

Dar, M. A.; Varshney, Dinesh

2018-02-01

Nanocrystalline samples of Zn0.94Mn0.06O and transition metal (TM) doped Zn0.94Mn0.01TM0.05O (TM = Co, Ni, and Cu) were prepared by sol-gel auto combustion method. X-ray diffraction (XRD) pattern infers that all synthesized samples except Zn0.94Mn0.01Ni0.05O and Zn0.94Mn0.01Cu0.05O with secondary phases of NiO and CuO are in single phase with hexagonal wurtzite structure (P63mc space group). Raman spectroscopy reveals four vibrational phonon modes are centered at 331, 380, 410, and 438 cm-1, assigned as E2 (H)-E2(L), A1(TO), E1(TO), and E1(LO) modes, respectively. A Raman spectrum of Zn0.94Mn0.01TM0.05O is entirely different from undoped Zn0.94Mn0.06O sample. Also, the infrared spectrum of transition metal doped samples is completely different from undoped Zn0.94Mn0.06O. Similar spectra are observed for Zn0.94Mn0.01Co0.05O, Zn0.94Mn0.01NiO, Zn0.94Mn0.01Cu0.05O and Zn0.94Mn0.01Zn0.05O samples. It was found that the band gap of Zn0.94Mn0.06O increased from 3.19 to 3.25eV by doping 5% transition metal oxide. Improved dielectric constant and reduced dielectric loss is measured for Zn0.94Mn0.01Ni/Cu0.05O as compared to Zn0.94Mn0.06O.

Effect of Fe doping on the electrochemical capacitor behavior of MnO2 nanocrystals

NASA Astrophysics Data System (ADS)

Poonguzhali, R.; Shanmugam, N.; Gobi, R.; Senthilkumar, A.; Viruthagiri, G.; Kannadasan, N.

2015-10-01

In this work, the influence of Fe doping on the capacitance behavior of MnO2 nanoparticles synthesized by chemical precipitation was investigated. During the doping process the concentration of Fe was increased from 0.025 M to 0.125 M in steps of 0.025 M. The products obtained were characterized by X-ray diffraction, Fourier infrared spectroscopy, scanning electron microscopy and N2 adsorption-desorption isotherms. To demonstrate the suitability of Fe-doped MnO2 for capacitor applications, cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance were recorded. Among the different levels of doping, the specific capacitance of 912 F/g was delivered by 0.075 M of Fe-doped MnO2 at a scan rate of 10 mV/s, which is almost more than fourfold that of the bare MnO2 electrode (210 F/g). Moreover, for the same concentration the charge, discharge studies revealed the highest specific capacitance of 1084 F/g at a current density of 10 A/g.

High-temperature thermoelectric properties of Ca0.92La0.04RE0.04MnO3 (RE = Sm, Dy and Yb) prepared by coprecipitation

NASA Astrophysics Data System (ADS)

Li, Cuiqin; Chen, Qianlin; Yan, Yunan; Li, Yanan; Zhao, Ying

2018-02-01

A series of Ca0.92La0.04RE0.04MnO3 (RE = Sm, Dy and Yb) compounds are synthesized via a coprecipitation technique. The influence of La/RE dual doping on the phase structure, microstructure and thermoelectric properties of the CaMnO3 system is investigated. Increased material density with grain sizes of 1-2 μm and a homogeneous microstructure is realized. Dual doping decreases the electrical resistivity due to an increase in the carrier concentration and also decreases the thermal conductivity due to increased grain scattering, damping of local vibrations by heavier La/RE ions compared to Ca and lattice distortion. The Ca0.92La0.04Yb0.04MnO3 shows the highest power factor of 3.49 × 10-4 W m-1 K-2 and the highest dimensionless figure of merit ZT of 0.25 at 770 K, which is approximately 3 times larger than that obtained for the undoped CaMnO3 and significantly larger than that of single-doped CaMnO3 prepared by solid-state reaction. This work provides a basic foundation for the industrial application of this thermoelectric material.

Crystal structure and thermoelectric properties of Sr–Mo substituted CaMnO3: a combined experimental and computational study† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5tc02318a

PubMed Central

Srivastava, D.; Azough, F.; Combe, E.; Funahashi, R.; Kepaptsoglou, D. M.; Ramasse, Q. M.; Molinari, M.; Yeandel, S. R.; Baran, J. D.

2015-01-01

A combination of experimental and computational techniques has been employed to study doping effects in perovskite CaMnO3. High quality Sr–Mo co-substituted CaMnO3 ceramics were prepared by the conventional mixed oxide route. Crystallographic data from X-ray and electron diffraction showed an orthorhombic to tetragonal symmetry change on increasing the Sr content, suggesting that Sr widens the transition temperature in CaMnO3 preventing phase transformation-cracking on cooling after sintering, enabling the fabrication of high density ceramics. Atomically resolved imaging and analysis showed a random distribution of Sr in the A-site of the perovskite structure and revealed a boundary structure of 90° rotational twin boundaries across {101}orthorhombic; the latter are predominant phonon scattering sources to lower the thermal conductivity as suggested by molecular dynamics calculations. The effect of doping on the thermoelectric properties was evaluated. Increasing Sr substitution reduces the Seebeck coefficient but the power factor remains high due to improved densification by Sr substitution. Mo doping generates additional charge carriers due to the presence of Mn3+ in the Mn4+ matrix, reducing electrical resistivity. The major impact of Sr on thermoelectric behaviour is the reduction of the thermal conductivity as shown experimentally and by modelling. Strontium containing ceramics showed thermoelectric figure of merit (ZT) values higher than 0.1 at temperatures above 850 K. Ca0.7Sr0.3Mn0.96Mo0.04O3 ceramics exhibit enhanced properties with S 1000K = –180 μV K–1, ρ 1000K = 5 × 10–5 Ωm, k 1000K = 1.8 W m–1 K–1 and ZT ≈ 0.11 at 1000 K. PMID:28496979

The magnetic, electrical transport and magnetoresistance properties of epitaxial La0.7Sr0.3Mn1- xFexO3 (x = 0-0.20) thin films prepared by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Huang, Q.; Li, Z. W.; Li, J.; Ong, C. K.

2001-05-01

High-quality epitaxial La0.7Sr0.3Mn1- xFexO3 (LSMFO) thin films have been successfully prepared on SrTiO3 single-crystal substrates by pulsed laser deposition. No structural changes were observed for x≤0.12. For x = 0.2, an elongation in the a-axis direction was identified. An antiferromagnetic arrangement of Fe and Mn ions over the whole Fe-doping region and a canted spin structure at x≥0.12 were observed. Unlike the case for the bulks, only one resistivity peak was observed for the epitaxial films. This shows that one of the two resistivity peaks for polycrystalline LSMFO bulks has its origin in grain boundaries. The effect of Fe doping can be attributed to a combination of doping disorder, Fe-Mn superexchange interactions and a site-percolation mechanism, which suppress the metallic conduction and ferromagnetism. In epitaxial LSMFO thin films, extrinsic magnetoresistance (MR) related to grain boundary effects was excluded. The intrinsic MR is gradually enhanced with increasing Fe concentration. For the film with x = 0.12, a fairly large MR = 12% was observed in a small field of 4 kOe at 145 K. For those films, the resistivity above Tc (the ferromagnetic Curie temperature) follows the Emin-Holstein model for small polarons. The polaron activation energy is enhanced due to weakening of the local double-exchange ferromagnetism by Fe doping. The fitting results indicate that the lattice polarons are magnetic in nature and that non-nearest-neighbour polaron hopping exists. The resistivity below Tp (the resistivity peak temperature) follows an empirical relation, ρ(T,H) = ρ0 + ρ2(H)T2 + ρ7.5(H)T7.5. It is found that the MR arises mainly from the suppression of T7.5-terms. The enhanced MR can be attributed to the suppression of the enhanced magnetic scattering and polaron scattering under an external field.

Chemo-sensors development based on low-dimensional codoped Mn2O3-ZnO nanoparticles using flat-silver electrodes.

PubMed

Rahman, Mohammed M; Gruner, George; Al-Ghamdi, Mohammed Saad; Daous, Muhammed A; Khan, Sher Bahadar; Asiri, Abdullah M

2013-03-28

Semiconductor doped nanostructure materials have attained considerable attention owing to their electronic, opto-electronic, para-magnetic, photo-catalysis, electro-chemical, mechanical behaviors and their potential applications in different research areas. Doped nanomaterials might be a promising owing to their high-specific surface-area, low-resistances, high-catalytic activity, attractive electro-chemical and optical properties. Nanomaterials are also scientifically significant transition metal-doped nanostructure materials owing to their extraordinary mechanical, optical, electrical, electronic, thermal, and magnetic characteristics. Recently, it has gained significant interest in manganese oxide doped-semiconductor materials in order to develop their physico-chemical behaviors and extend their efficient applications. It has not only investigated the basic of magnetism, but also has huge potential in scientific features such as magnetic materials, bio- & chemi-sensors, photo-catalysts, and absorbent nanomaterials. The chemical sensor also displays the higher-sensitivity, reproducibility, long-term stability, and enhanced electrochemical responses. The calibration plot is linear (r2 = 0.977) over the 0.1 nM to 50.0 μM 4-nitrophenol concentration ranges. The sensitivity and detection limit is ~4.6667 μA cm-2 μM-1 and ~0.83 ± 0.2 nM (at a Signal-to-Noise-Ratio, SNR of 3) respectively. To best of our knowledge, this is the first report for detection of 4-nitrophenol chemical with doped Mn2O3-ZnO NPs using easy and reliable I-V technique in short response time. As for the doped nanostructures, NPs are introduced a route to a new generation of toxic chemo-sensors, but a premeditate effort has to be applied for doped Mn2O3-ZnO NPs to be taken comprehensively for large-scale applications, and to achieve higher-potential density with accessible to individual chemo-sensors. In this report, it is also discussed the prospective utilization of Mn2O3-ZnO NPs on the basis of carcinogenic chemical sensing, which could also be applied for the detection of hazardous chemicals in ecological, environmental, and health care fields.

Chemo-sensors development based on low-dimensional codoped Mn2O3-ZnO nanoparticles using flat-silver electrodes

PubMed Central

2013-01-01

Background Semiconductor doped nanostructure materials have attained considerable attention owing to their electronic, opto-electronic, para-magnetic, photo-catalysis, electro-chemical, mechanical behaviors and their potential applications in different research areas. Doped nanomaterials might be a promising owing to their high-specific surface-area, low-resistances, high-catalytic activity, attractive electro-chemical and optical properties. Nanomaterials are also scientifically significant transition metal-doped nanostructure materials owing to their extraordinary mechanical, optical, electrical, electronic, thermal, and magnetic characteristics. Recently, it has gained significant interest in manganese oxide doped-semiconductor materials in order to develop their physico-chemical behaviors and extend their efficient applications. It has not only investigated the basic of magnetism, but also has huge potential in scientific features such as magnetic materials, bio- & chemi-sensors, photo-catalysts, and absorbent nanomaterials. Results The chemical sensor also displays the higher-sensitivity, reproducibility, long-term stability, and enhanced electrochemical responses. The calibration plot is linear (r2 = 0.977) over the 0.1 nM to 50.0 μM 4-nitrophenol concentration ranges. The sensitivity and detection limit is ~4.6667 μA cm-2 μM-1 and ~0.83 ± 0.2 nM (at a Signal-to-Noise-Ratio, SNR of 3) respectively. To best of our knowledge, this is the first report for detection of 4-nitrophenol chemical with doped Mn2O3-ZnO NPs using easy and reliable I-V technique in short response time. Conclusions As for the doped nanostructures, NPs are introduced a route to a new generation of toxic chemo-sensors, but a premeditate effort has to be applied for doped Mn2O3-ZnO NPs to be taken comprehensively for large-scale applications, and to achieve higher-potential density with accessible to individual chemo-sensors. In this report, it is also discussed the prospective utilization of Mn2O3-ZnO NPs on the basis of carcinogenic chemical sensing, which could also be applied for the detection of hazardous chemicals in ecological, environmental, and health care fields. PMID:23537000

Microstructural and optical properties of Mn doped NiO nanostructures synthesized via sol-gel method

NASA Astrophysics Data System (ADS)

Shah, Shamim H.; Khan, Wasi; Naseem, Swaleha; Husain, Shahid; Nadeem, M.

2018-04-01

Undoped and Mn(0, 5%, 10% and 15%) doped NiO nanostructures were synthesized by sol-gel method. Structure, morphology and optical properties were investigated through XRD, FTIR, SEM/EDS and UV-visible absorption spectroscopy techniques. XRD data analysis reveals the single phase nature with cubic crystal symmetry of the samples and the average crystallite size decreases with the doping of Mn ions upto 10%. FTIR spectra further confirmed the purity and composition of the synthesized samples. The non-spherical shape of the nanostructures was observed from SEM micrographs and gain size of the nanostructures reduces with Mn doping in NiO, whereas agglomeration increases in doped sample. Optical band gap was estimated using Tauc'srelation and found to increase on incorporation of Mn upto 10% in host lattice and then decreases for further doping.

An insight into the origin of room-temperature ferromagnetism in SnO2 and Mn-doped SnO2 quantum dots: an experimental and DFT approach.

PubMed

Manikandan, Dhamodaran; Boukhvalov, D W; Amirthapandian, S; Zhidkov, I S; Kukharenko, A I; Cholakh, S O; Kurmaev, E Z; Murugan, Ramaswamy

2018-02-28

SnO 2 and Mn-doped SnO 2 single-phase tetragonal crystal structure quantum dots (QDs) of uniform size with control over dopant composition and microstructure were synthesized using the high pressure microwave synthesis technique. On a broader vision, we systematically investigated the influence of dilute Mn ions in SnO 2 under the strong quantum confinement regime through various experimental techniques and density functional theoretical (DFT) calculations to disclose the physical mechanism governing the observed ferromagnetism. DFT calculations revealed that the formation of the stable (001) surface was much more energetically favorable than that of the (100) surface, and the formation energy of the oxygen vacancies in the stable (001) surface was comparatively higher in the undoped SnO 2 QDs. X-ray photoelectron spectroscopy (XPS) and first-principles modeling of doped QDs revealed that the lower doping concentration of Mn favored the formation of MnO-like (Mn 2+ ) structures in defect-rich areas and the higher doping concentration of Mn led to the formation of multiple configurations of Mn (Mn 2+ and Mn 3+ ) in the stable surfaces of SnO 2 QDs. Electronic absorption spectra indicated the characteristic spin allowed ligand field transitions of Mn 2+ and Mn 3+ and the red shift in the band gap. DFT calculations clearly indicated that only the substitutional dopant antiferromagnetic configurations were more energetically favorable. The gradual increase of magnetization at a low level of Mn-doping could be explained by the prevalence of antiferromagnetic manganese-vacancy pairs. Higher concentrations of Mn led to the appearance of ferromagnetic interactions between manganese and oxygen vacancies. The increase in the concentration of metallic dopants caused not just an increase in the total magnetic moment of the system but also changed the magnetic interactions between the magnetic moments on the metal ions and oxygen. The present study provides new insight into the fundamental understanding of the origin of ferromagnetism in transition metal-doped QDs.

Superconductivity, critical current density, and flux pinning in MgB2-x(SiC)x/2 superconductor after SiC nanoparticle doping

NASA Astrophysics Data System (ADS)

Dou, S. X.; Pan, A. V.; Zhou, S.; Ionescu, M.; Wang, X. L.; Horvat, J.; Liu, H. K.; Munroe, P. R.

2003-08-01

We investigated the effect of SiC nanoparticle doping on the crystal lattice structure, critical temperature Tc, critical current density Jc, and flux pinning in MgB2 superconductor. A series of MgB2-x(SiC)x/2 samples with x=0-1.0 were fabricated using an in situ reaction process. The contraction of the lattice and depression of Tc with increasing SiC doping level remained rather small most likely due to the counterbalancing effect of Si and C co-doping. The high level Si and C co-doping allowed the creation of intragrain defects and highly dispersed nanoinclusions within the grains which can act as effective pinning centers for vortices, improving Jc behavior as a function of the applied magnetic field. The enhanced pinning is mainly attributable to the substitution-induced defects and local structure fluctuations within grains. A pinning mechanism is proposed to account for different contributions of different defects in MgB2-x(SiC)x/2 superconductors.

Influence of Ce Doping on Structural and Transport Properties of Ca1- x Ce x MnO3 ( x=0.2) Manganite

NASA Astrophysics Data System (ADS)

Varshney, Dinesh; Mansuri, Irfan

2011-01-01

We have investigated structural, electric, magnetic and thermal transport properties of electron doped Ca1- x Ce x MnO3 ( x=0.2) manganites. The Cerium substitution for Ca2+causes electron doping into insulating CaMnO3 without e g electron. At room temperature the polycrystalline Ca0.8Ce0.2MnO3 is in the crystallographic orthorhombic structure, with Pnma space group symmetry from the refinement of x-ray powder diffraction patterns. The electrical resistivity data infers that Ca0.8Ce0.2MnO3 manganite is in the semiconducting phase. A smooth linear behavior of log plot values is obtained and is well fitted with adiabatic small polaron conduction model. Nearest-neighbor hopping of a small polaron leads to a mobility with a thermally activated form. The negative values of thermopower infer electron as carriers in Ca0.8Ce0.2MnO3. From susceptibility measurements the Ce doped CaMnO3 shows a transition from antiferromagnetic (AFM) to paramagnetic (PM) phase.

Cerium and zinc: Dual-doped LiMn 2O 4 spinels as cathode material for use in lithium rechargeable batteries

NASA Astrophysics Data System (ADS)

Thirunakaran, R.; Sivashanmugam, A.; Gopukumar, S.; Rajalakshmi, R.

Pristine spinel lithium manganese oxide (LiMn 2O 4) and zinc- and cerium-doped lithium manganese oxide [LiZn xCe yMn 2- x- yO 4 (x = 0.01-0.10; y = 0.10-0.01)] are synthesized for the first time via the sol-gel route using p-amino benzoic acid as a chelating agent to obtain micron-sized particles and enhanced electrochemical performance. The sol-gel route offers shorter heating time, better homogeneity and control over stoichiometry. The resulting spinel product is characterized through various methods such as thermogravimetic and differential thermal analysis (TG/DTA), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrochemical galvanostatic cycling studies. Charge-discharge studies of LiMn 2O 4 samples heated at 850 °C exhibit a discharge capacity of 122 mAh g -1 and a corresponding 99% coulombic efficiency in the 1st cycle. The discharge capacity and cycling performance of LiZn 0.01Ce 0.01Mn 1.98O 4 is found to be superior (124 mAh g -1), with a low capacity fade (0.1 mAh g -1 cycle -1) over the investigated 10 cycles.

Crystallite size strain analysis of nanocrystalline La0.7Sr0.3MnO3 perovskite by Williamson-Hall plot method

NASA Astrophysics Data System (ADS)

Kumar, Dinesh; Verma, Narendra Kumar; Singh, Chandra Bhal; Singh, Akhilesh Kumar

2018-04-01

The nanocrystalline Sr-doped LaMnO3 (La0.7Sr0.3MnO3 = LSMO) perovskite manganites having different crystallite size were synthesized using the nitrate-glycine auto-combustion method. The phase purity of the manganites was checked by X-ray diffraction (XRD) measurement. The XRD patterns of the sample reveal that La0.7S0.3MnO3 crystallizes into rhombohedral crystal structure with space group R-3c. The size-dependence of structural lattice parameters have been investigated with the help of Rietveld refinement. The structural parameters increase as a function of crystallite size. The crystallite-size and internal strain as a function of crystallite-size have been calculated using Williamson-Hall plot.

In-situ synchrotron x-ray study of MgB2 formation when doped by SiC

NASA Astrophysics Data System (ADS)

Abrahamsen, A. B.; Grivel, J.-C.; Andersen, N. H.; Herrmann, M.; Häßler, W.; Birajdar, B.; Eibl, O.; Saksl, K.

2008-02-01

We have studied the evolution of the reaction xMg + 2B + ySiC → zMg1-p(B1-qCq)2 + yMg2Si in samples of 1, 2, 5 and 10 wt% SiC doping. We found a coincident formation of MgB2 and Mg2Si, whereas the crystalline part of the SiC nano particles is not reacting at all. Evidence for incorporation of carbon into the MgB2 phase was established from the decrease of the a-axis lattice parameter upon increasing SiC doping. An estimate of the MgB2 lower limit grain size was found to decrease from L100 = 795 Å and L002 = 337 Å at 1 wt% SiC to L100 = 227 Å and L002= 60 Å at 10 wt% SiC. Thus superconductivity might be suppressed at 10 wt% SiC doping due to the grain size approaching the coherence length.

High-Performance Asymmetric Supercapacitors of MnCo2O4 Nanofibers and N-Doped Reduced Graphene Oxide Aerogel.

PubMed

Pettong, Tanut; Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Sukha, Phansiri; Sirisinudomkit, Pichamon; Seubsai, Anusorn; Chareonpanich, Metta; Kongkachuichay, Paisan; Limtrakul, Jumras; Sawangphruk, Montree

2016-12-14

The working potential of symmetric supercapacitors is not so wide because one type of material used for the supercapacitor electrodes prefers either positive or negative charge to both charges. To address this problem, a novel asymmetrical supercapacitor (ASC) of battery-type MnCo 2 O 4 nanofibers (NFs)//N-doped reduced graphene oxide aerogel (N-rGO AE ) was fabricated in this work. The MnCo 2 O 4 NFs at the positive electrode store the negative charges, i.e., solvated OH - , while the N-rGO AE at the negative electrode stores the positive charges, i.e., solvated K + . An as-fabricated aqueous-based MnCo 2 O 4 //N-rGO AE ASC device can provide a wide operating potential of 1.8 V and high energy density and power density at 54 W h kg -1 and 9851 W kg -1 , respectively, with 85.2% capacity retention over 3000 cycles. To understand the charge storage reaction mechanism of the MnCo 2 O 4 , the synchrotron-based X-ray absorption spectroscopy (XAS) technique was also used to determine the oxidation states of Co and Mn at the MnCo 2 O 4 electrode after being electrochemically tested. The oxidation number of Co is oxidized from +2.76 to +2.85 after charging and reduced back to +2.75 after discharging. On the other hand, the oxidation state of Mn is reduced from +3.62 to +3.44 after charging and oxidized to +3.58 after discharging. Understanding in the oxidation states of Co and Mn at the MnCo 2 O 4 electrode here leads to the awareness of the uncertain charge storage mechanism of the spinel-type oxide materials. High-performance ASC here in this work may be practically used in high-power applications.

Enhancing the superconducting temperature of MgB2 by SWCNT dilution

NASA Astrophysics Data System (ADS)

Ma, Danhao; Jayasingha, Ruwantha; Hess, Dustin T.; Adu, Kofi W.; Sumanasekera, Gamini U.; Terrones, Mauricio

2014-02-01

We report, for the first time, an increase in the superconducting critical temperature, TC of commercial “dirty” MgB2 by a nonsubstitutional hole-doping of the MgB2 structure using minute, single-wall carbon nanotube (SWCNT) inclusions. We varied the SWCNTs concentration from 0.05 wt% to 5 wt% and investigated the temperature-dependent resistivity from 10 K to 300 K. We used micro-Raman spectroscopy, field-emission scanning electron microscopy, and X-ray diffraction to analyze the interfacial interactions between the SWCNTs and the MgB2 grains. We obtained an increase in TC from 33.0 to 37.8 K (ΔTC+=4.8 K), which is attributed to charge transfer from the MgB2 structure to the SWCNT structure. The charge transfer phenomenon is confirmed by micro-Raman analysis of the phonon states of the SWCNT tangential band frequency in the composites. We determined the charge transfer per carbon atom to be 0.0023/C, 0.0018/C and 0.0008/C for 0.05 wt%, 0.5 wt% and 5 wt% SWCNT inclusions, respectively, taking into account the contributions from the softening of the lattice constant and the nonadiabatic (dynamic) effects at the Fermi level. This report provides an experimental, alternative pathway to hole-doping of MgB2 without appealing to chemical substitution.

Nitrogen-doped hollow porous carbon nanospheres coated with MnO2 nanosheets as excellent sulfur hosts for Li-S batteries

NASA Astrophysics Data System (ADS)

Zhang, Xiaolong; Yang, He; Guo, Junling; Zhao, Shupeng; Gong, Shoutao; Du, Xinyu; Zhang, Fengxiang

2017-11-01

In this work, nitrogen-doped hollow porous carbon nanospheres coated with MnO2 nanosheets (NHPC@MnO2) were prepared as a novel sulfur host for the cathode of lithium-sulfur battery. N-doping of carbon and deposition of the inherently polar MnO2 promote chemical binding of the host with sulfur and its reduction products, known as polysulfides. Meanwhile, proper N-doping can improve the electron conductivity of carbon, and the nanosheet structure may help to guarantee facile electron- and lithium-ion transport through MnO2. Attributed to these advantages, the NHPC@MnO2/S cathode with a high sulfur content (70 wt% and 2.6 mg cm-2) exhibited an excellent cycle stability: its capacity retention was 93% within 100 cycles at 0.5 C. It also displayed a good rate capability: discharge capacities being ˜1130 mAh g-1 at 0.2 C, ˜1000 mAh g-1 at 0.5 C, ˜820 mAh g-1 at 1 C, and ˜630 mAh g-1 at 2 C. Our work demonstrates the synergistic effect of MnO2 nanostructure and N-doped carbon nanospheres for enhanced performance of lithium-sulfur battery cathodes.

Charge and magnetic ordering in the electron-doped magnetoresistive materials CaMnO3-δ (δ=0.06,0.11)

NASA Astrophysics Data System (ADS)

Wiebe, C. R.; Greedan, J. E.; Gardner, J. S.; Zeng, Z.; Greenblatt, M.

2001-08-01

The magnetoresistive ``electron''-doped materials CaMnO3-δ (δ=0.06,0.11) have been investigated using powder neutron diffraction. The two materials are n-type semiconductors which exhibit antiferromagnetic ordering at TN~125 K, but they have different magnetic structures. The CaMnO2.94 sample orders in a simple G-type antiferromagnetic structure, which is also observed in CaMnO3. The CaMnO2.89 sample, on the other hand, exhibits two magnetic features: the G-type reflections as noted above, and a set of reflections that can be indexed on a k=(0,0,14) ordering wave vector. A model for the magnetic structure is proposed which involves Mn3+/Mn4+ charge ordering concomitant with the magnetic ordering. The presence of a set of weak, temperature independent structural reflections which can also be indexed on a k=(0,0,14) supercell suggests an oxygen vacancy ordering which may play a role in the charge ordering.

Synthesis and structural characterization of transition metal doped MgO: Mg0.95Mn0.01TM0.04O (TM = Co, Ni, Cu)

NASA Astrophysics Data System (ADS)

Islam, Ishtihadah; Khandy, Shakeel Ahmad; Hafiz, Aurangzeb Khurram

2018-05-01

In the present work, preparation and characterization of transition metal doped MgO: Zn0.94Mn0.01TM0.05O (TM = Co, Ni and Cu) nano-particles have been reported. Transition metal doped samples of MgO were synthesized by Sol gel auto combustion method. Structural characterisation from XRD and SEM show the formation of single-phase primary particles, nearly of spherical shaped nano-crystallites. The crystallite size was found to be 78.2, 67.02, 78.11 and 64 nm for pure, Co, Cu and Ni doped MgMnO nano-particles, respectively. Hence, the average crystallite size increases monotonously from Co to Cu doping.

Fabrication of Mg-X-O (X = Fe, Co, Ni, Cr, Mn, Ti, V, and Zn) barriers for magnetic tunnel junctions

NASA Astrophysics Data System (ADS)

Yakushiji, K.; Kitagawa, E.; Ochiai, T.; Kubota, H.; Shimomura, N.; Ito, J.; Yoda, H.; Yuasa, S.

2018-05-01

We fabricated magnetic tunnel junctions with a 3d-transition material(X)-doped MgO (Mg-X-O) barrier, and evaluated the effect of the doping on magnetoresistance (MR) and microstructure. Among the variations of X (X = Fe, Co, Ni, Cr, Mn, Ti, V, and Zn), X = Fe and Mn showed a high MR ratio of more than 100%, even at a low resistance-area product of 3 Ωμm2. The microstructure analysis revealed that (001) textured orientation formed for X = Fe and Mn despite substantial doping (about 10 at%). The elemental mappings indicated that Fe atoms in the Mg-Fe-O barrier were segregated at the interfaces, while Mn atoms were evenly involved in the Mg-Mn-O barrier. This suggests that MgO has high adaptability for Fe and Mn dopants in terms of high MR ratio.

Optimized spherical manganese oxide-ferroferric oxide-tin oxide ternary composites as advanced electrode materials for supercapacitors.

PubMed

Zhu, Jian; Tang, Shaochun; Vongehr, Sascha; Xie, Hao; Meng, Xiangkang

2015-09-18

Inexpensive MnO2 is a promising material for supercapacitors (SCs), but its application is limited by poor electrical conductivity and low specific surface area. We design and fabricate hierarchical MnO2-based ternary composite nanostructures showing superior electrochemical performance via doping with electrochemically active Fe3O4 in the interior and electrically conductive SnO2 nanoparticles in the surface layer. Optimization composition results in a MnO2-Fe3O4-SnO2 composite electrode material with 5.9 wt.% Fe3O4 and 5.3 wt.% SnO2, leading to a high specific areal capacitance of 1.12 F cm(-2) at a scan rate of 5 mV s(-1). This is two to three times the values for MnO2-based binary nanostructures at the same scan rate. The low amount of SnO2 almost doubles the capacitance of porous MnO2-Fe3O4 (before SnO2 addition), which is attributed to an improved conductivity and remaining porosity. In addition, the optimal ternary composite has a good rate capability and an excellent cycling performance with stable capacitance retention of ~90% after 5000 charge/discharge cycles at 7.5 mA cm(-2). All-solid-state SCs are assembled with such electrodes using polyvinyl alcohol/Na2SO4 electrolyte. An integrated device made by connecting two identical SCs in series can power a light-emitting diode indicator for more than 10 min.

Optimized spherical manganese oxide-ferroferric oxide-tin oxide ternary composites as advanced electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Zhu, Jian; Tang, Shaochun; Vongehr, Sascha; Xie, Hao; Meng, Xiangkang

2015-09-01

Inexpensive MnO2 is a promising material for supercapacitors (SCs), but its application is limited by poor electrical conductivity and low specific surface area. We design and fabricate hierarchical MnO2-based ternary composite nanostructures showing superior electrochemical performance via doping with electrochemically active Fe3O4 in the interior and electrically conductive SnO2 nanoparticles in the surface layer. Optimization composition results in a MnO2-Fe3O4-SnO2 composite electrode material with 5.9 wt.% Fe3O4 and 5.3 wt.% SnO2, leading to a high specific areal capacitance of 1.12 F cm-2 at a scan rate of 5 mV s-1. This is two to three times the values for MnO2-based binary nanostructures at the same scan rate. The low amount of SnO2 almost doubles the capacitance of porous MnO2-Fe3O4 (before SnO2 addition), which is attributed to an improved conductivity and remaining porosity. In addition, the optimal ternary composite has a good rate capability and an excellent cycling performance with stable capacitance retention of ˜90% after 5000 charge/discharge cycles at 7.5 mA cm-2. All-solid-state SCs are assembled with such electrodes using polyvinyl alcohol/Na2SO4 electrolyte. An integrated device made by connecting two identical SCs in series can power a light-emitting diode indicator for more than 10 min.

Electronic, optical and photocatalytic behavior of Mn, N doped and co-doped TiO{sub 2}: Experiment and simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Ya Fei; Li, Can, E-mail: canli1983@gmail.com; Lu, Song

2016-03-15

The crystal phase structure, surface morphology, chemical states and optical properties of Mn, N mono-doped and co-doped TiO{sub 2} nanoparticles were investigated by X-ray powder diffractometry, Raman spectra, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–vis diffuse reflectance spectroscopy. Meanwhile, geometry structures, formation energies, electronic and optical properties of all systems have been also analyzed by density functional theory. The results showed that the band gap values and the carrier mobility in the valence band, conduction band and impurity levels have a synergetic influence on the visible-light absorption and photocatalytic activity of the doped TiO{sub 2}. The number and themore » carrier mobility of impurity level jointly influence the photocatalytic activity of catalyst under visible-light. Especially, the photocatalytic activity of Mn-2N co-doped TiO{sub 2} beyond three-fold than that of pure TiO{sub 2} under visible-light. - Graphical abstract: The ILs formed by N-2p orbital in N single doped specimen lie above the VB, while the ILs formed by Mn-3d orbital in Mn single doped specimen appear below the CB. However, a large amount of ILs formed by N-2p orbital and Mn-3d orbital in N and Mn codoped specimens. The band gap values and the carrier mobility in the valence band, conduction band and impurity levels have a synergetic influence on the visible-light absorption and photocatalytic activity of the doped TiO{sub 2}. The number and the carrier mobility of impurity level jointly influence the photocatalytic activity of catalyst under visible-light.« less

Leakage current phenomena in Mn-doped Bi(Na,K)TiO{sub 3}-based ferroelectric thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walenza-Slabe, J.; Gibbons, B. J., E-mail: brady.gibbons@oregonstate.edu

2016-08-28

Mn-doped 80(Bi{sub 0.5}Na{sub 0.5})TiO{sub 3}-20(Bi{sub 0.5}K{sub 0.5})TiO{sub 3} thin films were fabricated by chemical solution deposition on Pt/TiO{sub 2}/SiO{sub 2}/Si substrates. Steady state and time-dependent leakage current were investigated from room temperature to 180 °C. Undoped and low-doped films showed space-charge-limited current (SCLC) at high temperatures. The electric field marking the transition from Ohmic to trap-filling-limited current increased monotonically with Mn-doping. With 2 mol. % Mn, the current was Ohmic up to 430 kV/cm, even at 180 °C. Modeling of the SCLC showed that all films exhibited shallow trap levels and high trap concentrations. In the regime of steady state leakage, theremore » were also observations of negative differential resistivity and positive temperature coefficient of resistivity near room temperature. Both of these phenomena were confined to relatively low temperatures (below ∼60 °C). Transient currents were observed in the time-dependent leakage data, which was measured out to several hundred seconds. In the undoped films, these were found to be a consequence of oxygen vacancy migration modulating the electronic conductivity. The mobility and thermal activation energy for oxygen vacancies was extracted as μ{sub ion} ≈ 1.7 × 10{sup −12} cm{sup 2} V{sup −1} s{sup −1} and E{sub A,ion} ≈ 0.92 eV, respectively. The transient current displayed different characteristics in the 1 mol. % Mn-doped films which were not readily explained by oxygen vacancy migration.« less

The EPR study of Mn(2+) ion doped DADT single crystal produced under high pressure and temperature.

PubMed

Ceylan, Ümit; Tapramaz, Recep

2016-01-05

An EPR study on Cu(2+) and VO(2+) doped di ammonium d-tartrate single crystals has been reported in previous papers, but the same host did not accept Mn(2+) ion at the same reaction conditions in previous trials. In this study EPR study of Mn(2+) ion doped di ammonium d tartrate single crystal, (DADT) [(NH4)2C4H4O6], produced in a reactor under high pressure and high temperature. The electronic transitions were determined by the optical absorption spectrum. Hyperfine splitting and g values of the Mn(2+) ion forming a complex in the lattice were measured from experimental spectra and spin-spin dipolar splitting parameters D and E were found by the spectrum simulation techniques. Copyright © 2015 Elsevier B.V. All rights reserved.

Incorporation of Mn2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Zhang, Chenguang; Liu, Shaowen; Liu, Xingwei; Deng, Fei; Xiong, Yan; Tsai, Fang-Chang

2018-03-01

A photoelectric conversion efficiency (PCE) of 4.9% was obtained under 100 mW cm-2 illumination by quantum-dot-sensitized solar cells (QDSSCs) using a CdS/Mn : CdSe sensitizer. CdS quantum dots (QDs) were deposited on a TiO2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn2+ doping into CdSe QDs is an innovative and simple method-chemical bath co-deposition, that is, mixing the Mn ion source with CdSe precursor solution for Mn : CdSe QD deposition. Compared with the CdS/CdSe sensitizer without Mn2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn2+ doping on the chemical, physical and photovoltaic properties of the QDSSCs were investigated by energy dispersive spectrometry, absorption spectroscopy, photocurrent density-voltage characteristics and electrochemical impedance spectroscopy. Mn-doped CdSe QDs in QDSSCs can obtain superior light absorption, faster electron transport and slower charge recombination than CdSe QDs.

Phase transition and multicolor luminescence of Eu{sup 2+}/Mn{sup 2+}-activated Ca{sub 3}(PO{sub 4}){sub 2} phosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Kai; Chen, Daqin, E-mail: dqchen@fjirsm.ac.cn; Xu, Ju

2014-01-01

Graphical abstract: We have synthesized Eu{sup 2+} doped and Eu{sup 2+}/Mn{sup 2+} co-doped Ca{sub 3}(PO{sub 4}){sub 2} phosphors. The emitting color varies from blue to green with increasing of Eu{sup 2+} content for the Eu{sup 2+}-doped phosphor, and the quantum yield of the 0.05Eu{sup 2+}: Ca{sub 2.95}(PO{sub 4}){sub 2} sample reaches 56.7%. Interestingly, Mn{sup 2+} co-doping into Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} leads to its phase transition from orthorhombic to rhombohedral, and subsequently generates tunable multi-color luminescence from green to red via Eu{sup 2+} → Mn{sup 2+} energy transfer. - Highlights: • A series of novel Eu{sup 2+}: Ca{submore » 3}(PO{sub 4}){sub 2} phosphors were successfully synthesized. • Phase transition of Ca{sub 3}(PO{sub 4}){sub 2} from orthorhombic to rhombohedral occurred when Mn{sup 2+} ions were doped. • The phosphors exhibited tunable multi-color luminescence. • The quantum yield of 0.05Eu{sup 2+}: Ca{sub 2.95}(PO{sub 4}){sub 2} phosphor can reach 56.7%. • The analyses of phosphors were carried out by many measurements. - Abstract: Intense blue-green-emitting Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} and tunable multicolor-emitting Eu{sup 2+}/Mn{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} phosphors are prepared via a solid-state reaction route. Eu{sup 2+}-doped orthorhombic Ca{sub 3}(PO{sub 4}){sub 2} phosphor exhibits a broad emission band in the wavelength range of 400–700 nm with a maximum quantum yield of 56.7%, and the emission peak red-shifts gradually from 479 to 520 nm with increase of Eu{sup 2+} doping content. Broad excitation spectrum (250–420 nm) of Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} matches well with the near-ultraviolet LED chip, indicating its potential applications as tri-color phosphors in white LEDs. Interestingly, Mn{sup 2+} co-doping into Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} leads to its phase transition from orthorhombic to rhombohedral, and subsequently generates tunable multi-color luminescence from green to red via Eu{sup 2+} → Mn{sup 2+} energy transfer, under 365 nm UV lamp excitation.« less

Effect of CTAB concentration on synthesis of nickel doped manganese oxide nanoparticles

NASA Astrophysics Data System (ADS)

Shobana, R.; Saravanakumar, B.; Ravi, G.; Yuvakkumar, R.

2018-05-01

In this work the effect of concentration of cetyltrimethylammonium bromide (CTAB) in the synthesis of Nickel doped Manganese oxide (Ni-MnO2) nanoparticles have been carried out by adopting the sol-gel process. The synthesized products were characterized by XRD, Infra- Red (FTIR) and SEM analysis. The XRD confirms the formation of Ni-MnO2 nanoparticles illustrate peak at 31.4° with lattice plane (-231). The IR spectra correspond to the peak at 592 and 846 cm-1 attributed to the characteristics peak for Ni-MnO2 nanoparticles. The SEM images for all three Ni-MnO2 nanoparticles for different concentration of CTAB allows us to assess the formation route of nano tentacles from 10 mM, 30 mM and 50 mM. The configured nano tentacles of Ni-MnO2 nanoparticles presumably leads to more significantly change its properties, particularly in its electrochemical properties show the ways to be suitable candidates for supercapacitor, battery, photo catalytic and fuel cell applications.

Investigation of microstructure, electrical and photoluminescence behaviour of Ni-doped Zn0.96Mn0.04O nanoparticles: Effect of Ni concentration

NASA Astrophysics Data System (ADS)

Rajakarthikeyan, R. K.; Muthukumaran, S.

2017-07-01

ZnO, Zn0.96Mn0.04O and Ni-doped Zn0.96Mn0.04O nanoparticles with different Ni concentrations (0%, 2% and 4%) have been synthesized successfully by sol-gel method. The effects of Ni doping on the structural and optical properties were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-visible spectroscopy, Fourier transform infrared (FTIR) spectroscopy and photoluminescence (PL) spectroscopy. The XRD pattern confirmed the existence of single phase wurtzite-like hexagonal structure throughout the Ni concentrations without any additional phases. The substitution of Ni created the lattice distortion due to the disparity of ionic radius between Zn and Ni which reduced the crystallite size. The microscopic images showed that the size of ZnO nanoparticles reduced by Ni-doping while the shape remains almost spherical/hexagonal type. The electrical conductivity found to be maximum at Ni = 2% due to the availability of more charge carriers generated by Ni. The decrease of electrical conductivity at higher doping (Ni = 4%) is due to the fact that the generation of more defects. The enhanced band gap from 3.73 eV (Ni = 0%) to 3.79 eV (Ni = 4%) by the addition of Ni explained by Burstein-Moss effect. The change in infra-red (IR) intensity and full width at half maximum (FWHM) corresponding to the frequency around defect states were caused by the difference in the bond lengths that occurs when Ni ion replaces Zn ion. The observed blue band emission from 474 nm to 481 nm is due to a radiative transition of an electron from the deep donar level of Zni to an acceptor level of neutral VZn and the origin of green band may be due to oxygen vacancies and intrinsic defects. The tuning of the band gap and the visible emission bands by Ni doping concluded that Ni-doped Zn0.96Mn0.04O is suitable for various nano-photo-electronics applications.

Magnetization reversal properties of Pr{sub 1-x}(Gd/Nd){sub x}MnO{sub 3} (x=0.3, 0.5, 0.7)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biswas, Sanjay; Pal, Sudipta, E-mail: sudipta.pal@rediffmail.com; Bose, Esa

2015-06-24

We report measurements of the temperature dependent magnetic properties of single phase orthorhombic perovskites system associated with space group Pbnm compounds Pr{sub 1-x}(Gd/Nd){sub x}MnO{sub 3} (x=0.3, 0.5, 0.7). Magnetic properties radically changes with the doping of Gd or Nd. A magnetization reversal is observed below the Neel temperature (T{sub N}), in DC magnetization measurements (at 50 Oe) in the doped compounds. The reversal of magnetization may be due to the antiparallel coupling between the two magnetic sublattices (|Pr+ Gd/ Nd | and Mn). The hysteresis plot taken at 50K indicates a ferrimagnetic characteristic and existence of spin canting of ionsmore » in the magnetic sublattices.« less

Study of half-metallicity in BiMnxFe1-xO3

NASA Astrophysics Data System (ADS)

Ameer, Shaan; Jindal, Kajal; Tomar, Monika; Jha, Pradip K.; Gupta, Vinay

2018-05-01

Spin polarized calculations are performed to study the structural and electronic properties of Mn doped BiFeO3 (BMFO) using simplified local spin density approximation (LSDA) functional under density functional theory (DFT). The B-site doping concentration of Mn in BMFO considered to be 16.7 % (BiMn0.167Fe0.833O3). Density of states calculations are carried out for both ferromagnetic (FM) and anti-ferromagnetic (AFM) order in BMFO. The results predict that BMFO is a half metal for both FM and AFM BMFO with magnetization of 29.0000 µB/cell and 1.0000 µB/cell respectively. The ground state of BMFO is found to be antiferromagnetic and demonstrates BMFO to be a potential candidate for spintronic applications.

Synthesis and characterization of electron doped La{sub 0.85}Te{sub 0.15}MnO{sub 3} thin film grown on LaAlO{sub 3} substrate by pulsed laser deposition technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhat, Irshad, E-mail: bhat.amu85@gmail.com; Husain, Shahid; Patil, S. I.

2015-06-24

We report the structural, morphological and magneto-transport properties of electron doped La{sub 0.85}Te{sub 0.15}MnO{sub 3} (LTMO) thin film grown on (001) LaAlO{sub 3} single crystal substrate by pulsed laser deposition (PLD). X-ray diffraction (XRD) results confirm that the film has good crystalline quality, single phase, and c-axis orientation. The atomic force microscopy (AFM) results have revealed that the film consists of grains with the average size in a range of 20–30 nm and root-mean square (rms) roughness of 0.27nm. The resistivity versus temperature measurement exhibits an insulator to metal transition (MIT). We have noticed a huge value of magnetoresistance (∼93%)more » close to MIT in presence of 8T field. X-ray photoemission spectroscopy confirms the electron doping and suggests that Te ions could be in the Te{sup 4+} state, while the Mn ions stay in the Mn{sup 2+} and Mn{sup 3+} valence state.« less

Evaluation of persistent-mode operation in a superconducting MgB2 coil in solid nitrogen

NASA Astrophysics Data System (ADS)

Patel, Dipak; Hossain, Md Shahriar Al; See, Khay Wai; Qiu, Wenbin; Kobayashi, Hiroki; Ma, Zongqing; Kim, Seong Jun; Hong, Jonggi; Park, Jin Yong; Choi, Seyong; Maeda, Minoru; Shahabuddin, Mohammed; Rindfleisch, Matt; Tomsic, Mike; Xue Dou, Shi; Kim, Jung Ho

2016-04-01

We report the fabrication of a magnesium diboride (MgB2) coil and evaluate its persistent-mode operation in a system cooled by a cryocooler with solid nitrogen (SN2) as a cooling medium. The main purpose of SN2 was to increase enthalpy of the cold mass. For this work, an in situ processed carbon-doped MgB2 wire was used. The coil was wound on a stainless steel former in a single layer (22 turns), with an inner diameter of 109 mm and height of 20 mm without any insulation. The two ends of the coil were then joined to make a persistent-current switch to obtain the persistent-current mode. After a heat treatment, the whole coil was installed in the SN2 chamber. During operation, the resultant total circuit resistance was estimated to be <7.4 × 10-14 Ω at 19.5 K ± 1.5 K, which meets the technical requirement for magnetic resonance imaging application.

Dielectric characteristics of Mn-doped LaTiO3+δ ceramics

NASA Astrophysics Data System (ADS)

Chen, Yan; Cui, Yimin

A series of ceramic composites of Mn-doped La1- x MnxTiO3+ δ and LaMnxTi1- x O3+ δ (x = 0.1, 0.2) were synthesized by conventional solid-state reaction method. The low-frequency complex dielectric properties of the composites were investigated as functions of temperature (77 K <= T <= 360 K) and frequency (100 Hz <= f <= 1 MHz), respectively. The dielectric constant of A-site doped samples is higher than that of B-site doped samples. The loss tangent of low doped samples is much less than that of high doped samples. The A-site doped composites exhibit intrinsic dielectric response with a dielectric constant of 40 in the temperature below 250 K. Interestingly, the dielectric constants of B-site doped ceramics increase slightly in the temperature range from 77 to 360 K. And it is clearly observed that extraordinarily high dielectric loss tangent ( 6) appear at low frequency (100 Hz) in LaMn0.2Ti0.8O3+ δ , which is 8 times larger than that of LaMn0.1Ti0.9O3+ δ , which indicates that the doped content can affect the intrinsic dielectric characteristics significantly.

Crab-shell induced synthesis of ordered macroporous carbon nanofiber arrays coupled with MnCo2O4 nanoparticles as bifunctional oxygen catalysts for rechargeable Zn-air batteries.

PubMed

Bin, Duan; Guo, Ziyang; Tamirat, Andebet Gedamu; Ma, Yuanyuan; Wang, Yonggang; Xia, Yongyao

2017-08-10

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out using noble metals (such as Pt) and metal oxides (such as RuO 2 and IrO 2 ) as catalysts, respectively. Nevertheless, several key issues such as high cost, poor stability, and detrimental environmental effects limit the catalytic activity of these noble metal- and metal oxide-based catalysts. Herein, we have designed and synthesized macroporous carbon nanofiber arrays by using a natural crab shell template. Subsequently, spinel MnCo 2 O 4 nanoparticles were embedded into the nitrogen-doped macroporous carbon nanofiber arrays (NMCNAs) by a hydrothermal method. Accompanied by the good conductivity, large surface area and doping of nitrogen, the as-prepared MnCo 2 O 4 /NMCNA exhibited remarkable catalytic performance and outstanding stability for both ORR and OER in alkaline media. The macroporous superstructures play vital role in reducing the ion transport resistance and facilitating the diffusion of gaseous products (O 2 ). Finally, rechargeable Zn-air batteries using the MnCo 2 O 4 /NMCNA catalyst displayed appreciably lower overpotentials, higher power density and better stability than commercial Pt/C, thus raising the prospect of functional low-cost, non-precious-metal bifunctional catalysts in metal-air batteries.

Mn2- x Y x (MoO4)3 Phosphor Excited by UV GaN-Based Light-Emitting Diode for White Emission

NASA Astrophysics Data System (ADS)

Chen, Lung-Chien; Tseng, Zong-Liang; Hsu, Ting-Chun; Yang, Shengyi; Chen, Yuan-Bin

2017-04-01

One option for low-cost white light-emitting diodes (LEDs) is the combination of a near-ultraviolet (UV) LED chip (382 nm) and a single phosphor. Such Mn2- x Y x (MoO4)3 single phosphors have been fabricated by a simple solid-state reaction route and their emission color tuned by controlling the Mn doping amount. The chromaticity coordinates of the white light emitted by the UV GaN LED with the MnY(MoO4)3 phosphor were x = 0.5204 and y = 0.4050 [correlated color temperature (CCT) = 7958 K].

Thermoelectric and Magnetic Properties of Ca0.98RE0.02MnO3- δ (RE = Sm, Gd, and Dy)

NASA Astrophysics Data System (ADS)

Bhaskar, Ankam; Liu, Chia-Jyi; Yuan, J. J.

2012-09-01

Polycrystalline samples of Ca0.98RE0.02MnO3- δ (RE = Sm, Gd, and Dy) have been prepared by conventional solid-state reactions and their properties measured at 300 K to 700 K. All samples were single phase with orthorhombic structure. The average valence and oxygen content of Ca0.98RE0.02MnO3- δ were determined by iodometric titration. Doping at the Ca site by rare-earth metals causes a strong decrease of electrical resistivity due to the creation of charge carrier content by Mn3+ in the Mn4+ matrix, as evidenced by iodometric titration results. The Seebeck coefficient of all the samples was negative, indicating that the predominant carriers are electrons over the entire temperature range. Among the doped samples, Ca0.98Dy0.02MnO3- δ had the highest dimensionless figure of merit of 0.073 at 612 K, representing an improvement of about 115% with respect to the undoped CaMnO3- δ sample at the same temperature. All the samples exhibited an antiferromagnetic transition with Néel temperature of around 120 K. Magnetization measurements indicated that Ca0.98RE0.02 MnO3- δ samples exhibited a high-spin state of Mn3+.

Flux pinning in nanoparticle doped MgB 2/Cu tapes

NASA Astrophysics Data System (ADS)

Babić, E.; Kušević, I.; Husnjak, O.; Soltanian, S.; Wang, X. L.; Dou, S. X.

2007-09-01

The irreversibility fields Birr and critical current densities Jc of undoped and Si and SiC nanoparticle doped (5, 10 and 20 wt%) MgB2 tapes were measured in the temperature (T) range 2-38 K and in magnetic fields B ⩽ 16 T. Whereas Birr of undoped tapes varies smoothly with T, those of doped tapes show a change in slope around a crossover field Bcr which increases with nanoparticle content and also depends on their type. This indicates matching effect in vortex pinning, probably associated with Mg2Si nanoprecipitates formed during heat treatment. Indeed, Birr of doped tapes was enhanced in respect to that of undoped one with the highest enhancement for Birr ≈ Bcr, but the enhancement remained high ≈1.4 even for Birr ≫ Bcr (low temperatures). The variations of Jc and the pinning force density Fp = JcB with B and T support the above findings.

Thermodynamic Stability of Transition Metal Substituted LiMn 2-xMxO 4 (M=Cr, Fe, Co, and Ni) Spinels

NASA Astrophysics Data System (ADS)

Lai, Chenying

The formation enthalpies from binary oxides of LiMn2O 4, LiMn2-xCrxO4 (x = 0.25, 0.5, 0.75 and 1), LiMn2-xFexO4 (x = 0.25 and 0.5), LiMn2-xCoxO4 (x = 0.25, 0.5, and 0.75) and LiMn1.75Ni 0.25O4 at 25 °C have been measured by high-temperature oxide-melt-solution calorimetry and were found to be strongly exothermic. Increasing Cr, Co and Ni content leads to more thermodynamically stable spinels, but increasing Fe content does not significantly affect the stability. The formation enthalpies from oxides of the fully substituted spinels, LiMnMO 4 (M = Cr, Fe and Co) become more exothermic (implying increasing stability) with decreasing ionic radius of the metal and lattice parameters of the spinel. The trend in enthalpy versus metal content is roughly linear, suggesting a close-to-zero heat of mixing in LiMn2O4 - LiMnMO 4 solid solutions. These data confirm that transition metal doping is beneficial for stabilizing these potential cathode materials for lithium-ion batteries.

Growth and electrical properties of (Mn,F) co-doped 0.92Pb(Zn 1/3Nb 2/3)O 3-0.08PbTiO 3 single crystal

NASA Astrophysics Data System (ADS)

Zhang, Shujun; Lebrun, Laurent; Randall, Clive A.; Shrout, Thomas R.

2004-06-01

The growth and characterization of (Mn,F) doped Pb(Zn 1/3Nb 2/3)O 3-PbTiO 3 (PZNT) single crystals are reported in this paper. The typical single crystal obtained is up to 30 mm size with dark brown color. The crystal lattice parameters of doped PZNT crystal are slightly decreased compared to the pure one. The room temperature dielectric permittivity along <0 0 1> direction is about 6000, which is lower than that of the pure PZNT8 because of the dopants. The Curie temperature of the doped crystal is about 180°C while the ferroelectric phase transition temperature is around 100°C, which are higher than those of the pure PZNT8 single crystal. The remnant polarization and coercive field of <0 0 1> oriented doped crystal measured at 1 Hz and 10 kV/cm field are about 27 μC/cm 2 and 4.2 kV/cm, respectively. The room temperature mechanical quality factor is ˜300. Piezoelectric coefficient of <0 0 1> oriented doped crystal is higher than 3500 pC/N and the longitudinal electromechanical coupling factor is larger than 93%. The piezoelectric properties of doped PZNT single crystal with temperature and orientations are also reported in this paper. The valence state of the manganese dopant was determined by electron spin resonance, indicating no Mn 4+ in the crystals, suggesting the valence of manganese ions in PZNT crystals may be 2+, which acts as a hardener, stabilizes the domain wall and pins the domain wall motion, on the other hand, the dopant will enter Ti 4+ position, shifting the crystal composition to higher PT content.

Synthesis of ultrathin nitrogen-doped graphitic carbon nanocages as advanced electrode materials for supercapacitor.

PubMed

Tan, Yueming; Xu, Chaofa; Chen, Guangxu; Liu, Zhaohui; Ma, Ming; Xie, Qingji; Zheng, Nanfeng; Yao, Shouzhuo

2013-03-01

Synthesis of nitrogen-doped carbons with large surface area, high conductivity, and suitable pore size distribution is highly desirable for high-performance supercapacitor applications. Here, we report a novel protocol for template synthesis of ultrathin nitrogen-doped graphitic carbon nanocages (CNCs) derived from polyaniline (PANI) and their excellent capacitive properties. The synthesis of CNCs involves one-pot hydrothermal synthesis of Mn3O4@PANI core-shell nanoparticles, carbonization to produce carbon coated MnO nanoparticles, and then removal of the MnO cores by acidic treatment. The CNCs prepared at an optimum carbonization temperature of 800 °C (CNCs-800) have regular frameworks, moderate graphitization, high specific surface area, good mesoporosity, and appropriate N doping. The CNCs-800 show high specific capacitance (248 F g(-1) at 1.0 A g(-1)), excellent rate capability (88% and 76% capacitance retention at 10 and 100 A g(-1), respectively), and outstanding cycling stability (~95% capacitance retention after 5000 cycles) in 6 M KOH aqueous solution. The CNCs-800 can also exhibit great pseudocapacitance in 0.5 M H2SO4 aqueous solution besides the large electrochemical double-layer capacitance. The excellent capacitance performance coupled with the facile synthesis of ultrathin nitrogen-doped graphitic CNCs indicates their great application potential in supercapacitors.

Facile fabrication of MnO x and N co-doped hierarchically porous carbon microspheres for high-performance supercapacitors

DOE PAGES

Yang, Ying; Yang, Feng; Lee, Sungsik; ...

2016-01-16

Facile fabrication of manganese oxide (MnO x, 0 < x < 2) and nitrogen (N) co-doped carbon microspheres (MnO x-N-CS) has been firstly developed by one-pot construction of Mn-functionalized melamine-formaldehyde (Mn-MF) resin spheres before pyrolysis. The resulting hybrids bear evenly dispersed MnO x and N moieties in situ anchored on hierarchically porous carbon microspheres formed simultaneously. The capacitive performance is greatly tailored by varying the Mn/melamine molar ratio in the synthetic mixture and pyrolysis temperature. It is found that the MnO x-N-CS hybrid (0.008 wt% Mn, pyrolyzed at 800 °C) exhibits the highest specific capacitance up to 258 F gmore » –1 at a scan rate of 1 mV s –1 (in 6 M KOH), and keeps a high capacitance retention ratio of 98% after 5000 cycles. The synergism between MnO x, N moieties and carbon spheres proves to be responsible for the remarkably improved performance, as compared to the pure carbon sphere and MnO x (N)-doped carbon sphere. Lastly, the well-developed MnO x-N-CS hybrids highlight the great potentials for widespread supercapacitor applications.« less

Microwave Absorption Properties of La0.8Ca0.2-xAgxMnO3 (x=0.05; x=0.15) Synthesized by Sol-Gel Method

NASA Astrophysics Data System (ADS)

Kurniawan, B.; Laksmi, W.; Sahara, N. A.

2018-04-01

Microwave absorption properties of La0.8Ca0.2-xAgxMnO3 (x= 0.05; 0.15) is reported in this paper. Lanthanum manganite materials was reported as a potential absorber material [1][2][3]. In this paper, the material was synthesized by sol-gel method, calcined at 550°C, and sintered at 900°C. The material was characterized by X-Ray Diffractometer (XRD), and we found that the materials were single phased. Through SEM-EDS characterization it is found that the materials have compositional purity. The resistivity of the materials is obtained by four point probe method, and it is shown that Ag doped decreases the resistivity of the materials. Reflection loss of La0.8Ca0.15Ag0.05MnO3 reaches -4.470 dB and La0.8Ca0.05Ag0.15MnO3 reaches - 7.953 dB.

LaAlO3:Mn4+ as Near-Infrared Emitting Persistent Luminescence Phosphor for Medical Imaging: A Charge Compensation Study

PubMed Central

De Clercq, Olivier Q.; Korthout, Katleen

2017-01-01

Mn4+-activated phosphors are emerging as a novel class of deep red/near-infrared emitting persistent luminescence materials for medical imaging as a promising alternative to Cr3+-doped nanomaterials. Currently, it remains a challenge to improve the afterglow and photoluminescence properties of these phosphors through a traditional high-temperature solid-state reaction method in air. Herein we propose a charge compensation strategy for enhancing the photoluminescence and afterglow performance of Mn4+-activated LaAlO3 phosphors. LaAlO3:Mn4+ (LAO:Mn4+) was synthesized by high-temperature solid-state reaction in air. The charge compensation strategies for LaAlO3:Mn4+ phosphors were systematically discussed. Interestingly, Cl−/Na+/Ca2+/Sr2+/Ba2+/Ge4+ co-dopants were all found to be beneficial for enhancing LaAlO3:Mn4+ luminescence and afterglow intensity. This strategy shows great promise and opens up new avenues for the exploration of more promising near-infrared emitting long persistent phosphors for medical imaging. PMID:29231901

Synergistic effect of N-decorated and Mn2+ doped ZnO nanofibers with enhanced photocatalytic activity

PubMed Central

Wang, Yuting; Cheng, Jing; Yu, Suye; Alcocer, Enric Juan; Shahid, Muhammad; Wang, Ziyuan; Pan, Wei

2016-01-01

Here we report a high efficiency photocatalyst, i.e., Mn2+-doped and N-decorated ZnO nanofibers (NFs) enriched with vacancy defects, fabricated via electrospinning and a subsequent controlled annealing process. This nanocatalyst exhibits excellent visible-light photocatalytic activity and an apparent quantum efficiency up to 12.77%, which is 50 times higher than that of pure ZnO. It also demonstrates good stability and durability in repeated photocatalytic degradation experiments. A comprehensive structural analysis shows that high density of oxygen vacancies and nitrogen are introduced into the nanofibers surface. Hence, the significant enhanced visible photocatalytic properties for Mn-ZnO NFs are due to the synergetic effects of both Mn2+ doping and N decorated. Further investigations exhibit that the Mn2+-doping facilitates the formation of N-decorated and surface defects when annealing in N2 atmosphere. N doping induce the huge band gap decrease and thus significantly enhance the absorption of ZnO nanofibers in the range of visible-light. Overall, this paper provides a new approach to fabricate visible-light nanocatalysts using both doping and annealing under anoxic ambient. PMID:27600260

Rectifying and photovoltaic properties of the heterojunction composed of CaMnO3 and Nb-doped SrTiO3

NASA Astrophysics Data System (ADS)

Sun, J. R.; Zhang, S. Y.; Shen, B. G.; Wong, H. K.

2005-01-01

A heterojunction composed of CaMnO3 (CMO) and Nb-doped SrTiO3 (STON) was fabricated and its properties were studied and compared with La0.67Ca0.33MnO3/STON and LaMnO3+δ/STON p-n, junctions. This CMO/STON junction exhibits an asymmetric current-voltage relation similar to a p-n junction. The most remarkable discovery is that the magnetic state of the manganites has a strong impact on the rectifying behaviors. The diffusion voltage, which is the critical voltage for the current rush, shows a tendency to decrease/increase with the establishment of the antiferromagnetic/ferromagnetic order in the manganites of the junction. Similar to other manganite p-n junctions, CMO/STON also exhibits a significant photovoltaic effect, and the maximum photovoltage is ˜2.2mV under the illumination of ˜7mW light (λ=460nm). A qualitative explanation is given based on an analysis on the band diagram of the junctions.

Electronic and magnetic properties of Mn-doped WSe2 monolayer under strain

NASA Astrophysics Data System (ADS)

Xin, Qianqian; Zhao, Xu; Wang, Tianxing

2017-04-01

Electronic and magnetic properties of Mn-doped WSe2 monolyer subject to isotropic strain are investigated using the first-principles methods based on the density functional theory. Our results indicate that Mn-doped WSe2 monolayer is a magnetic semiconductor nanomaterial with strong spontaneous magnetism without strain and the total magnetic moment of Mn-doped system is 1.038μB. We applied strain to Mn-doped WSe2 monolayer from -10% to 10%. The doped system transforms from magnetic semiconductor to half-metallic material from -10% to -2% compressive strain and from 2% to 6% tensile strain. The largest half-metallic gap is 0.450 eV at -2% compressive strain. The doped system shows metal property from 7% to 10%. Its maximum magnetic moment comes to 1.181μB at 6% tensile strain. However, the magnetic moment of system decreases to zero sharply when tensile strain arrived at 7%. Strain changes the redistribution of charges and arises to the magnetic effect. The coupling between the 3d orbital of Mn atom, 5d orbital of W atom and 4p orbital of Se atom is analyzed to explain the strong strain effect on the magnetic properties. Our studies predict Mn-doped WSe2 monolayers under strain to be candidates for thin dilute magnetic semiconductors, which is important for application in semiconductor spintronics.

Piezoelectric properties and temperature stability of Mn-doped Pb(Mg1/3Nb2/3)-PbZrO3-PbTiO3 textured ceramics

NASA Astrophysics Data System (ADS)

Yan, Yongke; Cho, Kyung-Hoon; Priya, Shashank

2012-03-01

In this letter, we report the electromechanical properties of textured 0.4Pb(Mg1/3Nb2/3)O3-0.25PbZrO3-0.35PbTiO3 (PMN-PZT) composition which has relatively high rhombohedral to tetragonal (R-T) transition temperature (TR-T of 160 °C) and Curie temperature (TC of 234 °C) and explore the effect of Mn-doping on this composition. It was found that MnO2-doped textured PMN-PZT ceramics with 5 vol. % BaTiO3 template (T-5BT) exhibited inferior temperature stability. The coupling factor (k31) of T-5BT ceramic started to degrade from 75 °C while the random counterpart showed a very stable tendency up to 180 °C. This degradation was associated with the "interface region" formed in the vicinity of BT template. MnO2 doped PMN-PZT ceramics textured with 3 vol. % BT and subsequently poled at 140 °C (T-3BT140) exhibited very stable and high k31 (>0.53) in a wide temperature range from room temperature to 130 °C through reduction in the interface region volume. Further, the T-3BT140 ceramic exhibited excellent hard and soft combinatory piezoelectric properties of d33 = 720 pC/N, k31 = 0.53, Qm = 403, tan δ = 0.3% which are very promising for high power and magnetoelectric applications.

An innovative concept of use of redox-active electrolyte in asymmetric capacitor based on MWCNTs/MnO2 and Fe2O3 thin films

PubMed Central

Chodankar, Nilesh R.; Dubal, Deepak P.; Lokhande, Abhishek C.; Patil, Amar M.; Kim, Jin H.; Lokhande, Chandrakant D.

2016-01-01

In present investigation, we have prepared a nanocomposites of highly porous MnO2 spongy balls and multi-walled carbon nanotubes (MWCNTs) in thin film form and tested in novel redox-active electrolyte (K3[Fe(CN)6] doped aqueous Na2SO4) for supercapacitor application. Briefly, MWCNTs were deposited on stainless steel substrate by “dip and dry” method followed by electrodeposition of MnO2 spongy balls. Further, the supercapacitive properties of these hybrid thin films were evaluated in hybrid electrolyte ((K3[Fe(CN)6 doped aqueous Na2SO4). Thus, this is the first proof-of-design where redox-active electrolyte is applied to MWCNTs/MnO2 hybrid thin films. Impressively, the MWCNTs/MnO2 hybrid film showed a significant improvement in electrochemical performance with maximum specific capacitance of 1012 Fg−1 at 2 mA cm−2 current density in redox-active electrolyte, which is 1.5-fold higher than that of conventional electrolyte (Na2SO4). Further, asymmetric capacitor based on MWCNTs/MnO2 hybrid film as positive and Fe2O3 thin film as negative electrode was fabricated and tested in redox-active electrolytes. Strikingly, MWCNTs/MnO2//Fe2O3 asymmetric cell showed an excellent supercapacitive performance with maximum specific capacitance of 226 Fg−1 and specific energy of 54.39 Wh kg−1 at specific power of 667 Wkg−1. Strikingly, actual practical demonstration shows lightning of 567 red LEDs suggesting “ready-to sell” product for industries. PMID:27982087

An innovative concept of use of redox-active electrolyte in asymmetric capacitor based on MWCNTs/MnO2 and Fe2O3 thin films.

PubMed

Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Patil, Amar M; Kim, Jin H; Lokhande, Chandrakant D

2016-12-16

In present investigation, we have prepared a nanocomposites of highly porous MnO 2 spongy balls and multi-walled carbon nanotubes (MWCNTs) in thin film form and tested in novel redox-active electrolyte (K 3 [Fe(CN) 6 ] doped aqueous Na 2 SO 4 ) for supercapacitor application. Briefly, MWCNTs were deposited on stainless steel substrate by "dip and dry" method followed by electrodeposition of MnO 2 spongy balls. Further, the supercapacitive properties of these hybrid thin films were evaluated in hybrid electrolyte ((K 3 [Fe(CN) 6 doped aqueous Na 2 SO 4 ). Thus, this is the first proof-of-design where redox-active electrolyte is applied to MWCNTs/MnO 2 hybrid thin films. Impressively, the MWCNTs/MnO 2 hybrid film showed a significant improvement in electrochemical performance with maximum specific capacitance of 1012 Fg -1 at 2 mA cm -2 current density in redox-active electrolyte, which is 1.5-fold higher than that of conventional electrolyte (Na 2 SO 4 ). Further, asymmetric capacitor based on MWCNTs/MnO 2 hybrid film as positive and Fe 2 O 3 thin film as negative electrode was fabricated and tested in redox-active electrolytes. Strikingly, MWCNTs/MnO 2 //Fe 2 O 3 asymmetric cell showed an excellent supercapacitive performance with maximum specific capacitance of 226 Fg -1 and specific energy of 54.39 Wh kg -1 at specific power of 667 Wkg -1 . Strikingly, actual practical demonstration shows lightning of 567 red LEDs suggesting "ready-to sell" product for industries.

Synthesis and magnetic properties of tin spinel ferrites doped manganese

NASA Astrophysics Data System (ADS)

El Moussaoui, H.; Mahfoud, T.; Habouti, S.; El Maalam, K.; Ben Ali, M.; Hamedoun, M.; Mounkachi, O.; Masrour, R.; Hlil, E. K.; Benyoussef, A.

2016-05-01

In this work we report the synthesis, the microstructural characterization and the magnetic properties of tin spinel ferrites doped manganese (Sn1-xMnxFe2O4 with x=0.25, 0.5, 0.75, and 1) nanoparticles prepared by co-precipitation method. The effect of annealing temperature on the structure, morphology and magnetic properties of Sn0.5Mn0.5Fe2O4 has been investigated. The synthesized nanoparticle sizes have been controlled between 4 and 9 nm, with uniform spherical morphology as confirmed by transmission electron microscopy (TEM). All the samples prepared possess single domain magnetic. The nanoparticles of Sn0.5Mn0.5Fe2O4 with 4 nm in diameter have a blocking temperature close to 100 K. In addition, the cation distribution obtained from the X-ray diffraction of this sample was confirmed by magnetic measurement. For the Sn1-xMnxFe2O4; (0≤x≤1) samples, the magnetization and coercive fields increase when the augmentation of Mn content increases. For x=0.5, such parameters decrease when the calcination temperature increases.

Evolution of electrical properties and domain configuration of Mn modified Pb(In1/2Nb1/2)O3-PbTiO3 single crystals

NASA Astrophysics Data System (ADS)

Qiao, Huimin; He, Chao; Yuan, Feifei; Wang, Zujian; Li, Xiuzhi; Liu, Ying; Guo, Haiyan; Long, Xifa

2018-04-01

The acceptor doped relaxor-based ferroelectric materials are useful for high power applications such as probes in ultrasound-guided high intensity focused ultrasound therapy. In addition, a high Curie temperature is desired because of wider temperature usage and improved temperature stability. Previous investigations have focused on Pb(Mg1/3Nb2/3)O3-PbTiO3 and Pb(Zn1/3Nb2/3)O3-PbTiO3 systems, which have a ultrahigh piezoelectric coefficient and dielectric constant, but a relatively low Curie temperature. It is desirable to study the binary relaxor-based system with a high Curie temperature. Therefore, Pb(In1/2Nb1/2)O3-PbTiO3 (PINT) single crystals were chosen to study the Mn-doped influence on their electrical properties and domain configuration. The evolution of ferroelectric hysteresis loops for doped and virgin samples exhibit the pinning effect in Mn-doped PINT crystals. The relaxation behaviors of doped and virgin samples are studied by fit of the modified Curie-Weiss law and Volgel-Fucher relation. In addition, a short-range correlation length was fitted to study the behavior of polar nanoregions based on the domain configuration obtained by piezoresponse force microscopy. Complex domain structures and smaller short-range correlation lengths (100-150 nm for Mn-doped PINT and >400 nm for pure PINT) were obtained in the Mn-doped PINT single crystals.

Synthesis and characterization of nanosized lithium manganate and its derivatives

NASA Astrophysics Data System (ADS)

Iqbal, Muhammad Javed; Zahoor, Sabia

Spinel lithium manganese oxide, LiMn 2O 4 and its derivatives are prepared by the sol-gel method. The lattice constant of the pure material is calculated as 8.23 Å. Different transition metal cations of chromium, iron, cobalt, nickel, copper and zinc (0.05 and 0.15 M) are doped in place of manganese in the LiMn 2O 4. X-ray powder diffraction data show that the spinel framework preserved its integrity upon doping. Formation of a single phase and the purity of the samples are confirmed by X-ray powder diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). The crystallite size of the samples is calculated by use of the Scherrer formula and is found to be within a range of 43-66 nm. The electrical conductivity of the samples is determined over a temperature range of 200-300 K by means of four-point probe method. An increasing trend of conductivity with increase in temperature is noted for all the samples. The parent compound LiMn 2O 4 has a conductivity value of 3.47 × 10 -4 ohm -1 cm -1 at room temperature. This value increases on doping with the above-mentioned transition metal cations.

Correlation between microstructure and electrical transport properties of La0.7(Ba1-xCax)0.3MnO3 (x = 0 and 0.03) synthesized by sol-gel

NASA Astrophysics Data System (ADS)

Kurniawan, Budhy; Winarsih, Suci; Imaduddin, Agung; Manaf, Azwar

2018-03-01

In this paper, we reported the correlation of structure, microstructure, and electrical transport properties of polycrystalline La0.7(Ba1-xCax)0.3MnO3 (x = 0 and 0.03). The materials were synthesized by sol-gel method. These materials have interesting electronic and magnetic properties which are heavily affected by the degree of crystallographic mismatch between the La and Mn sites. By tuning these sites, the double exchange (DE) and Coulomb interactions among Mn ions can be artificially controlled. La0.7Ba0.3MnO3 is one of the strong candidates for application because it has high magnetoresistance and magnetocaloric properties. Doped Ca to the La0.7Ba0.3MnO3 is aimed for reducing its transition temperature to near room temperature and increasing the magnetoresistance and magnetocaloric properties of this material. Jahn-Teller distortion can be linked to core-shell model with the result of percolation model.

Synthesis and effect of Ce and Mn co-doping on photoluminescence characteristics of Ca6AlP5O20:Eu novel phosphors.

PubMed

Shinde, K N; Dhoble, S J

2013-01-01

A series of Ca6AlP5O20 doped with rare earths (Eu and Ce) and co-doped (Eu, Ce and Eu,Mn) were prepared by combustion synthesis. Under Hg-free excitation, Ca6AlP5O20:Eu exhibited Eu(2+) (486 nm) emission in the blue region of the spectrum and under near Hg excitation (245 nm), Ca6AlP5O20:Ce phosphor exhibited Ce(3+) emission (357 nm) in the UV range. Photoluminescence (PL) peak intensity increased in Ca6AlP5O20:Eu,Ce and Ca6AlP5O20:Eu, Mn phosphors due to co-activators of Ce(3+) and Mn(2+) ions. As a result, these ions played an important role in PL emission in the present matrix. Ca6AlP5O20:Eu, Ce and Ca6AlP5O20:Eu, Mn phosphors provided energy transfer mechanisms via Ce(3+) → Eu(2+) and Eu(2+) → Mn(2+), respectively. Eu ions acted as activators and Ce ions acted as sensitizers. Ce emission energy was well matched with Eu excitation energy in the case of Ca6AlP5O20:Eu, Ce and Eu ions acted as activators and Mn ions acted as sensitizers in Ca6AlP5O20:Eu, Mn. This study included synthesis of new and efficient phosphate phosphors. The impact of doping and co-doping on photoluminescence properties and energy transfer mechanisms were investigated and we propose a feasible interpretation. Copyright © 2012 John Wiley & Sons, Ltd.

Synthesis and property investigation of metal-based nanomaterials for biotechnological applications

NASA Astrophysics Data System (ADS)

Darsanasiri, Nalin Dammika

Luminescent lanthanide-based materials have drawn recent interest due to their applications in in vitro cellular imaging. Sensitive biological analysis requires optical labels with high water dispersibility & stability and excellent luminescent properties. Most literature reported lanthanide complexes with high luminescence intensity are hydrophobic and unstable, limiting their biological applications. This project was designed to incorporate a highly luminescent lanthanide beta-diketonate complex in a silica nanoparticle. Eu(btfa)3dmph complex was synthesized, which exhibits red luminescence at 614 nm with a narrow (15 nm) full with half-maximum (btfa=4,4,4-trifluoro-1-phenyl-1,3-butanedione, dmph=4,7-dimethyl,1,10-phenanthroline). A synthetic procedure was optimized to incorporate the Eu-complex in a silica-based nanoparticle with an average particle diameter of 36 nm. Eu-complex based silica nanoparticles exhibit high stability and water-dispersibility with a luminescence quantum yield of 10 %. The nanoparticles showed antimicrobial activity against clinically important E.coli, S.aureus and S.epidermidis. Synthesis, materials characterization, and antimicrobial studies of the complex and the nanoparticles was discussed in the first part of this thesis. Nanotechnology is emerging as a new interdisciplinary field combining biology, chemistry, physics, and material science. Recent advances promise developments in the synthesis, modification and practical applications of polymer-coated manganese (Mn)-based zinc oxide (ZnO) nanoparticles (NPs). The size distribution, shape, and surface modification of metal-based ZnO nanoparticles are the key factors determining their specific physical properties. Due to the strong antibacterial properties and low toxicity towards mammalian cells, ZnO NPs have been successfully used in a wide range of applications including wound dressing, protective clothing, antibacterial surfaces, food preservation, and cosmetics as biocidal and disinfecting agents. In this study, cotton textiles with antimicrobial activity were developed by incorporating polymer-coated Mn-doped ZnO nanoparticles. Antimicrobial potential of synthesized Mn-doped zinc oxide (ZnO) nanoparticles against two bacteria strains ( Escherichia coli as Gram-negative bacteria, Staphylococcus aureus as Gram-positive bacteria) in liquid and solid phases was studied in this work. Polymer-coated Mn-doped ZnO nanoparticles were prepared by the modified co-precipitation method. Characterization of the nanoparticles was carried out using Ultra-violet visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). The average particle size of the nanoparticles was found to be less than 15 nm. The antibacterial activity of the nanoparticles was evaluated using minimum inhibitory concentration (MIC) and agar diffusion method. Disk diffusion studies revealed that the nanoparticles have excellent antimicrobial activity against E.coli and S.aureus bacterial species. Therefore, it was concluded that the polymer-coated Mn-doped ZnO nanoparticles were excellent antibacterial agents with potential clinical applications.

Electrochemical synthesis of superconductive MgB 2 from molten salts

NASA Astrophysics Data System (ADS)

Yoshii, Kenji; Abe, Hideki

2003-05-01

We have found that superconductive MgB2 can be electrochemically synthesized from molten salts. The electrolysis was performed in an Ar flow at 600 °C on fused mixtures composed of MgCl2, MgB2O4, Na2B2O4 and alkali halides such as KCl, NaCl, and LiCl. Superconductivity was observed for a wide variety of electrolytes. It was also found that the magnetic and electrical transport properties are the most improved for samples prepared from MgCl2-NaCl-KCl-MgB2O4 electrolytes.

Improving the electrochemical performances of Li-rich Li1.20Ni0.13Co0.13Mn0.54O2 through a cooperative doping of Na+ and PO43- with Na3PO4

NASA Astrophysics Data System (ADS)

Liu, Yi; Ning, De; Zheng, Lirong; Zhang, Qinghua; Gu, Lin; Gao, Rui; Zhang, Jicheng; Franz, Alexandra; Schumacher, Gerhard; Liu, Xiangfeng

2018-01-01

Li-rich layered oxide cathodes suffer from poor rate capability, voltage decay and inferior cycling stability. Herein, we propose a novel synergistic strategy to improve the electrochemical performances of Li-rich Li1.20Ni0.13Co0.13Mn0.54O2 by the co-doping of Na+ and PO43-. The co-doping of Na+ for Li and PO43- for Mn is simultaneously achieved using Na3PO4 as a dopant. The co-doping of Na+ and PO43- not only enhances the high-rate performance (106.4 mAhg-1@10C) and capacity retention (93.8%@1C@100 cycles) but also mitigates the voltage decay owing to the synergistic effect of Na+ and PO43- co-doping. The synergistic mechanism is unraveled based on neutron diffraction, aberration-corrected scanning transmission electron microscope, X-ray photoelectron spectroscopy, ex-situ X-ray absorption spectra, ex-situ X-ray diffraction, electrochemical impedance spectroscopy and electrochemical measurements. The co-doping of Na+ and PO43- enlarges the interlayer spacing and suppresses Li/Ni mixing which increases Li+ diffusivity and enhances the rate capability. Meanwhile, the co-doping of Na+ and PO43- shrinks the thickness of the slabs, weakens the TM-O covalency and alleviates the volume change in the charge/discharge process which improves the layered structure stability and the cycling performances. This study presents some new insights into designing high performance cathode materials through a cooperative modulation of different crystal sites doping.

Microstructure and spectroscopic investigations of calcium zinc bismuth phosphate glass ceramics doped with manganese ions

NASA Astrophysics Data System (ADS)

Suneel Kumar, A.; Sambasiva Rao, M. V.; Chinna Ram, G.; Krishna Rao, D.

2018-01-01

Multi-component 10CaF2-20ZnO-(15 - x)Bi2O3-55P2O5:xMnO (0 ≤ x ≤ 2.5) glass ceramics were synthesised by melt quenching technique and heat treatment. The prepared glass ceramics were characterised by XRD, DTA, EDS and SEM. Spectroscopic studies such as optical absorption, EPR, FTIR and Raman were also carried out on these glass ceramics. The XRD and SEM studies have indicated that ceramic samples contain well defined and randomly distributed grains of different crystalline phases. The observed increase of enthalpy from DTA patterns up to 1 mol% of MnO indicates that the crystallisation starts initially from the surface of the material then gradually it is extended to the volume of the material and this influence is meagre at higher concentrations of MnO. The absorption spectra of manganese doped glass ceramics have exhibited two types of conventional bands; one due to Mn2+ ions and other due to Mn3+ ions. The EPR spectra of MnO doped glass ceramics showed a resonance signal around g2 = 2.023 with a six line hyperfine structure and another signal at about g1 = 4.314. The relative intensity and half-width of these two signals are observed to increase with the increase in the concentration of manganese ions up to 1 mol% beyond this concentration it is found to decrease. Such observation indicates the conversion of part of Mn2+ ions into Mn3+ ions in the glass ceramic matrix. The observed increase in the intensity of symmetrical structural units at the expense of asymmetrical structural units from the FTIR and Raman spectra at higher concentration of MnO indicating that Mn2+ ions occupy the network forming positions in the glass ceramic structure.

Effect of chromium doping on the structural and vibrational properties of Mn-Zn ferrites

NASA Astrophysics Data System (ADS)

Saleem, M.; Varshney, Dinesh

2018-05-01

The synthesis of Mn0.5Zn0.5-xCrxFe2O4 (x = 0.0, 0.1, 0.2 and 0.5) via sol-gel Auto-combustion technique is reported. The x-ray diffraction spectra analysis revealed the cubic spinel structure for all the prepared spinel ferrite samples with the space group Fd3m. The structural studies identify the decrease of lattice parameter however the crystallite size decreases on increasing the Cr concentration. The Raman spectrum reveals five active phonon modes at room temperature and shifting of modes toward the higher frequency side on moving from Mn-ZnFe2O4 to Mn-CrFe2O4.

Magnetocaloric effect in potassium doped lanthanum manganite perovskites prepared by a pyrophoric method

NASA Astrophysics Data System (ADS)

Das, Soma; Dey, T. K.

2006-08-01

The magnetocaloric effect (MCE) in fine grained perovskite manganites of the type La1-xKxMnO3 (0

Visible light absorbance enhanced by nitrogen embedded in the surface layer of Mn-doped sodium niobate crystals, detected by ultra violet - visible spectroscopy, x-ray photoelectron spectroscopy, and electric conductivity tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molak, A., E-mail: andrzej.molak@us.edu.pl; Pilch, M.

2016-05-28

Sodium niobate crystals doped with manganese ions, Na(NbMn)O{sub 3}, were annealed in a nitrogen N{sub 2} flow at 600, 670, and 930 K. It was verified that simultaneous doping with Mn ions and annealing in nitrogen enhanced the photocatalytic features of sodium niobate. The transmission in the ultraviolet-visible range was measured at room temperature. The absorbance edge is in the range from 3.4 to 2.3 eV. The optical band gap E{sub gap} = 1.2–1.3 eV was evaluated using the Tauc relation. Crystals annealed at 670 K and 930 K exhibited an additional shift of the absorption edge of ∼20–40 nm toward longer wavelengths. The optical energy gap narrowedmore » as a result of the superimposed effect of Mn and N co-doping. The x-ray photoelectron spectroscopy test showed that N ions incorporated into the surface layer. The valence band consisted of O 2p states hybridized with Nb 4d, Mn 3d, and N 2s states. The disorder detected in the surroundings of Nb and O ions decreased due to annealing. The binding energy of oxygen ions situated within the surface layer was E{sub B} ≈ 531 eV. The other contributions were assigned to molecular contamination. The contribution centered at 535.5 eV vanished after annealing at 600 K and 670 K. The contribution centered at 534 eV vanished after annealing at 930 K. The N{sub 2} annealing partly removed carbonates from the surfaces of the samples. In the 480–950 K range, the electric conductivity activation energy, E{sub a} = 0.7–1.2 eV, was comparable with the optical E{sub gap}. The electric permittivity showed dispersion in the 0.1–800 kHz range that corresponds to the occurrence of defects.« less

Crystal growth and crystal structures of six novel phases in the Mn/As/O/Cl(Br) system, as well as magnetic properties of α-Mn3(AsO4)2

NASA Astrophysics Data System (ADS)

Weil, Matthias; Kremer, Reinhard K.

2017-01-01

Chemical vapour transport reactions (900 °C → 820 °C, Cl2 or Br2 as transport agent) of in situ formed Mn3(AsO4)2 yielded the orthoarsenates(V) α-Mn3(AsO4)2 and β-Mn3(AsO4)2 as well as the oxoarsenate(V) halide compounds Mn7(AsO4)4Cl2, Mn11(AsO4)7Cl, Mn11(AsO4)7Br and Mn5(AsO4)3Cl. The crystal structures of all six phases were determined from single crystal X-ray diffraction data. The crystal structures of α-and β-Mn3(AsO4)2 are isotypic with the corresponding phosphate phases γ- and α-Mn3(PO4)2, respectively, and are reported here for the first time. A comparative discussion with other structures of general composition M3(AsO4)2 (M = Mg; divalent first-row transition metal) is given. The unique crystal structures of Mn7(AsO4)4Cl2 and that of the two isotypic Mn11(AsO4)7X (X = Cl, Br) structures are composed of two [MnO5] polyhedra, two [MnO4Cl2] polyhedra (one with site symmetry 1 bar), two AsO4 tetrahedra, and one [MnO5] polyhedron, three [MnO6] octahedra (one with site symmetry.m.), one [MnO4X], one [MnO5X] polyhedron and four AsO4 tetrahedra, respectively. The various polyhedra of the three arsenate(V) halides are condensed into three-dimensional framework structures by corner- and edge-sharing. Mn5(AsO4)3Cl adopts the chloroapatite structure. The magnetic and thermal properties of pure polycrystalline samples of a-Mn3(AsO4)2 were investigated in more detail. The magnetic susceptibility proves all Mn atoms to be in the oxidation state +2 yielding an effective magnetic moment per Mn atom of 5.9 μB. Long-range antiferromagnetic ordering is observed below 8.2 K consistent with the negative Curie-Weiss temperature of -50 K derived from the high temperature susceptibility data.

Incorporation of Mn2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells.

PubMed

Zhang, Chenguang; Liu, Shaowen; Liu, Xingwei; Deng, Fei; Xiong, Yan; Tsai, Fang-Chang

2018-03-01

A photoelectric conversion efficiency (PCE) of 4.9% was obtained under 100 mW cm -2 illumination by quantum-dot-sensitized solar cells (QDSSCs) using a CdS/Mn : CdSe sensitizer. CdS quantum dots (QDs) were deposited on a TiO 2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn 2+ doping into CdSe QDs is an innovative and simple method-chemical bath co-deposition, that is, mixing the Mn ion source with CdSe precursor solution for Mn : CdSe QD deposition. Compared with the CdS/CdSe sensitizer without Mn 2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn 2+ doping on the chemical, physical and photovoltaic properties of the QDSSCs were investigated by energy dispersive spectrometry, absorption spectroscopy, photocurrent density-voltage characteristics and electrochemical impedance spectroscopy. Mn-doped CdSe QDs in QDSSCs can obtain superior light absorption, faster electron transport and slower charge recombination than CdSe QDs.

Incorporation of Mn2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells

PubMed Central

Zhang, Chenguang; Liu, Shaowen; Liu, Xingwei; Deng, Fei

2018-01-01

A photoelectric conversion efficiency (PCE) of 4.9% was obtained under 100 mW cm−2 illumination by quantum-dot-sensitized solar cells (QDSSCs) using a CdS/Mn : CdSe sensitizer. CdS quantum dots (QDs) were deposited on a TiO2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn2+ doping into CdSe QDs is an innovative and simple method—chemical bath co-deposition, that is, mixing the Mn ion source with CdSe precursor solution for Mn : CdSe QD deposition. Compared with the CdS/CdSe sensitizer without Mn2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn2+ doping on the chemical, physical and photovoltaic properties of the QDSSCs were investigated by energy dispersive spectrometry, absorption spectroscopy, photocurrent density–voltage characteristics and electrochemical impedance spectroscopy. Mn-doped CdSe QDs in QDSSCs can obtain superior light absorption, faster electron transport and slower charge recombination than CdSe QDs. PMID:29657776

Effect of excess lithium in LiMn2O4 and Li1.15Mn1.85O4 electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhuo, Zengqing; Olalde-Velasco, Paul.; Chin, Timothy

We performed a comparative study of the soft x-ray absorption spectroscopy of the LiMn2O4 and Li1.15Mn1.85O4 electrode materials with a quantitative analysis of the Mn oxidation states. The revealed redox evolution of Mn upon the electrochemical cycling clarifies the effect of the excess Li in the materials, which naturally explains the different electrochemical performance. The spectral analysis perfectly agrees with the different initial cycling capacities of the two materials. The results show unambiguously that Mn3+ starts to dominate the electrode surface after only one cycle. More importantly, the data show that, while LiMn2O4 electrodes follow the nominal Mn redox evolution,more » the formation of Mn3+ on the electrode surface is largely retarded for the Li1.15Mn1.85O4 during most of the electrochemical process. Such a different surface Mn redox behavior leads to differences in the detrimental effects of Mn2+ formation on the surface, which is observed directly after only two cycles. Our results provide strong evidence that a key effect of the (bulk) excess Li doping is actually due to processes on the electrode surfaces.« less

Effect of excess lithium in LiMn2O4 and Li1.15Mn1.85O4 electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy

DOE PAGES

Zhuo, Zengqing; Olalde-Velasco, Paul.; Chin, Timothy; ...

2017-02-27

We performed a comparative study of the soft x-ray absorption spectroscopy of the LiMn2O4 and Li1.15Mn1.85O4 electrode materials with a quantitative analysis of the Mn oxidation states. The revealed redox evolution of Mn upon the electrochemical cycling clarifies the effect of the excess Li in the materials, which naturally explains the different electrochemical performance. The spectral analysis perfectly agrees with the different initial cycling capacities of the two materials. The results show unambiguously that Mn3+ starts to dominate the electrode surface after only one cycle. More importantly, the data show that, while LiMn2O4 electrodes follow the nominal Mn redox evolution,more » the formation of Mn3+ on the electrode surface is largely retarded for the Li1.15Mn1.85O4 during most of the electrochemical process. Such a different surface Mn redox behavior leads to differences in the detrimental effects of Mn2+ formation on the surface, which is observed directly after only two cycles. Our results provide strong evidence that a key effect of the (bulk) excess Li doping is actually due to processes on the electrode surfaces.« less

Site preference and compensation behavior in Co(Cr, Mn){sub 2}O{sub 4} system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, H. G.; College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124; Wang, Z.

Site preference of doped Mn ions in CoCr{sub 2−x}Mn{sub x}O{sub 4} (x = 0–2) series has been derived separately from structure and magnetic measurement. It shows that parts of the doped Mn ions occupy the A (Co) sites when x < 0.5. And then, it takes the two B (Cr) sites in turn before and after x = 1.3. This site preference behavior results in a role conversion of the magnetic contributors and, thus, leads to the composition dependent magnetic compensation. Temperature induced compensation and negative magnetization have also been found in several samples, which is attributed to the large energy barrier between the ferromagnetic andmore » antiferromagnetic spin arrangement. A structure transition from cubic to tetragonal symmetry has been detected.« less

Phase Separation and d Electronic Orbitals on Cyclic Degradation in Li-Mn-O Compounds: First-Principles Multiscale Modeling and Experimental Observations.

PubMed

Kim, Duho; Lim, Jin-Myoung; Park, Min-Sik; Cho, Kyeongjae; Cho, Maenghyo

2016-07-06

A combined study involving experiments and multiscale computational approaches is conducted to propose a theoretical solution for the suppression of the Jahn-Teller distortion which causes severe cyclic degradation. As-synthesized pristine and Al-doped Mn spinel compounds are the focus to understand the mechanism of the cyclic degradation in terms of the Jahn-Teller distortion, and the electrochemical performance of the Al-doped sample shows enhanced cyclic performance compared with that of the pristine one. Considering the electronic structures of the two systems using first-principles calculations, the pristine spinel suffers entirely from the Jahn-Teller distortion by Mn(3+), indicating an anisotropic electronic structure, but the Al-doped spinel exhibits an isotropic electronic structure, which means the suppressed Jahn-Teller distortion. A multiscale phase field model in nanodomain shows that the phase separation of the pristine spinel occurs to inactive Li0Mn2O4 (i.e., fully delithiated) gradually during cycles. In contrast, the Al-doped spinel does not show phase separation to an inactive phase. This explains why the Al-doped spinel maintains the capacity of the first charge during the subsequent cycles. On the basis of the mechanistic understanding of the origins and mechanism of the suppression of the Jahn-Teller distortion, fundamental insight for making tremendous cuts in the cyclic degradation could be provided for the Li-Mn-O compounds of Li-ion batteries.

Facile synthesis of a nitrogen-doped graphene flower-like MnO2 nanocomposite and its application in supercapacitors

NASA Astrophysics Data System (ADS)

Dong, Jinyang; Lu, Gang; Wu, Fan; Xu, Chenxi; Kang, Xiaohong; Cheng, Zhiming

2018-01-01

A flower-like MnO2 nanocomposite embedded in nitrogen-doped graphene (NG-MnO2) is fabricated by a hydrothermal method. It is a mesoporous nanomaterial with a pore size of approximately 0.765 cm3 g-1 and specific surface area of 201.8 m2 g-1. NG-MnO2 exhibits a superior average specific capacitance of 220 F g-1 at 0.5 A g-1 and a preferable capacitance of 189.1 F g-1, even at 10 A g-1. After 1000 cycles, over 98.3% of the original specific capacitance retention of the NG-MnO2 electrode is maintained, and it can even activate a red light emitting diode (LED) after being charged, which indicates that it has excellent cycling stability as an electrode material. This prominent electrochemical performance is primarily attributed to the nitrogen doping and mesoporous structures of NG-MnO2, which can be attributed to its numerous electroactive sites as well as faster ion and electron transfer for redox reactions than general graphene-MnO2 nanocomposites (G-MnO2).

Effect of sintering on structure and magnetic properties of Mn-doped Zn ferrite

NASA Astrophysics Data System (ADS)

Farheen, Atiya; Singh, Rajender

2018-05-01

The Mn-doped zinc ferrites, MnxZn1-xFe2O4 (x= 0 and 0.1) were prepared using co-precipitation method. The as-prepared samples were sintered at different temperatures. The x-ray diffraction pattern for all the samples confirms single phase spinel structure with Fd-3m space group. The lattice parameters have been estimated using Rietveld fitting. The magnetic moment is found to increase with Mn-doping. The magnetization increases as the sintering temperature increases up to 1200°C. The as-prepared samples are super paramagnetic, while the sintered samples are ferrimagnetic in nature.

Correlations of structural, magnetic, and dielectric properties of undoped and doped CaCu3Ti4O12

NASA Astrophysics Data System (ADS)

Krohns, S.; Lu, J.; Lunkenheimer, P.; Brizé, V.; Autret-Lambert, C.; Gervais, M.; Gervais, F.; Bourée, F.; Porcher, É. F.; Loidl, A.

2009-11-01

The present work reports synthesis, as well as a detailed and careful characterization of structural, magnetic, and dielectric properties of differently tempered undoped and doped CaCu3Ti4O12 (CCTO) ceramics. For this purpose, neutron and X-ray powder diffraction, SQUID measurements, and dielectric spectroscopy have been performed. Mn-, Fe-, and Ni-doped CCTO ceramics were investigated in great detail to document the influence of low-level doping with 3d metals on the antiferromagnetic structure and dielectric properties. In the light of possible magnetoelectric coupling in these doped ceramics, the dielectric measurements were also carried out in external magnetic fields up to 7 T. At low temperatures the dielectric constant shows a minor but significant dependence on the applied magnetic field. Undoped CCTO is well-known for its colossal dielectric constant in a broad frequency and temperature range. With the present extended characterization of doped as well as undoped CCTO, we want to address the question why doping with only 1% Mn or 0.5% Fe decreases the room-temperature dielectric constant of CCTO by a factor of ~100 with a concomitant reduction of the conductivity, whereas 0.5% Ni doping changes the dielectric properties only slightly. In addition, diffraction experiments and magnetic investigations were undertaken to check for possible correlations of the magnitude of the colossal dielectric constants with structural details or with magnetic properties like the magnetic ordering, the Curie-Weiss temperatures, or the paramagnetic moment. It is revealed, that while the magnetic ordering temperature and the effective moment of all investigated CCTO ceramics are rather similar, there is a dramatic influence of doping and tempering time on the Curie-Weiss constant.

Influence of Fe doped on the magnetocaloric behavior of La_{{2}/{3}} Ca_{{1}/{3}} Mn1-x Fe x O3 compounds: a Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Alzate-Cardona, J. D.; Barco-Rios, H.; Restrepo-Parra, E.

2018-02-01

The magnetocaloric behavior of La{2/{3}} Ca{1/{3}} Mn1-x Fe x O3 for x  =  0.00, 0.02, 0.03, 0.05, 0.07, 0.08 and 0.10 under the influence of an external magnetic field was simulated and analyzed. Simulations were carried out using the Monte Carlo method and the classical Heisenberg model under the Metropolis algorithm. These mixed valence manganites are characterized by having three types of magnetic ions corresponding to Mn4+≤ft(S=\\frac{3}{2}\\right) , which are bonded with Ca2+ , and Mneg3+ and Mneg\\prime3+ (S=2) , related to La3+ . The Fe ions were randomly included, replacing Mn ions. With this model, the magnetic entropy change, Δ S , in an isothermal process was determined. -Δ Sm showed maximum peaks around the paramagnetic-ferromagnetic transition temperature, which depends on Fe doping. Relative cooling power was computed for different Fe concentrations varying the magnetic applied field. Our model and results show that the Fe doping decreases the magnetocaloric effect in the La{2/{3}} Ca{1/{3}} Mn1-x Fe x O3, making this a bad candidate for magnetic refrigeration. The strong dependence of the magnetocaloric behavior on Fe doping and the external magnetic field in La{2/{3}} Ca{1/{3}} Mn1-x Fe x O3 can boost these materials for the future technological applications.

Effect of Nb and F co-doping on Li1.2Mn0.54Ni0.13Co0.13O2 cathode material for high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ming, Lei; Zhang, Bao; Cao, Yang; Zhang, Jia-Feng; Wang, Chun-Hui; Wang, Xiao-Wei; Li, Hui

2018-04-01

The Li1.2Mn0.54-xNbxCo0.13Ni0.13O2-6xF6x (x=0, 0.01, 0.03, 0.05) is prepared by traditional solid-phase method, and the Nb and F ions have been successfully doped into Mn and O sites of layered materials Li1.2Mn0.54Co0.13Ni0.13O2, respectively. The incorporating Nb ion in Mn site could effectively restrain the migration of transtion metal ions during long-term cycling, and keep the stability of the crystal structure. The Li1.2Mn0.54-xNbxCo0.13Ni0.13O2-6xF6x shows suppressed voltage fade and higher capacity retention of 98.1 after 200 cycles at rate of 1 C. The replacement of O2- by the strongly electronegative F- was beneficial for suppressed the structure change of Li2MnO3 from the eliminating of oxygen in initial charge process. Therefore, the initial coulomb efficiency of doped Li1.2Mn0.54-xNbxCo0.13Ni0.13O2-6xF6x gets improved, which is higher than that of pure Li1.2Mn0.54Co0.13Ni0.13O2. In addition, the Nb and F co-doping could effectively enhance the transfer of lithium-ion and electrons, and thus improving rate performance.

Crystal Structure, Piezoelectric and Dielectric Properties of (Li, Ce)4+, Nb5+ and Mn2+ Co-doped CaBi4Ti4O15 High-Temperature Ceramics

NASA Astrophysics Data System (ADS)

Xin, Deqiong; Chen, Qiang; Wu, Jiagang; Bao, Shaoming; Zhang, Wen; Xiao, Dingquan; Zhu, Jianguo

2016-07-01

Bismuth-layered structured ceramics Ca0.85(Li,Ce)0.075Bi4Ti4- x Nb x O15-0.01MnCO3 were prepared by the conventional solid-state reaction method. The evolution of microstructure and corresponding electrical properties were studied. All the samples presented a single bismuth layered-structural phase with m = 4, indicating that (Li, Ce)4+, Nb5+ and Mn2+ adequately enter into the pseudo-perovskite structure and form solid solutions. It was found that Ca0.85(Li,Ce)0.075Bi4Ti3.98Nb0.02O15-0.01MnCO3 (CBTLCM-0.02Nb) ceramics possess the optimum electrical properties. The piezoelectric coefficient d 33, dielectric constant ɛ r, loss tan δ, planar electromechanical coupling factor k p and Curie-temperature T C of CBTLCM-0.02Nb ceramics were found to be ˜19.6 pC/N, 160, 0.16%, 8.1% and 767°C, respectively. Furthermore, the thermal depoling behavior demonstrates that the d 33 value of x = 0.02 content remains at 16.8 pC/N after annealing at 500°C. These results suggest that the (Li, Ce)4+-, Nb5+- and Mn2+-doped CBT-based ceramics are promising candidates for high-temperature piezoelectric applications.

μSR study of Eu{sub 0.8}Ce{sub 0.2}Mn{sub 2}O{sub 5} and EuMn{sub 2}O{sub 5} multiferroics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vorob’ev, S. I., E-mail: vsiloa@pnpi.spb.ru; Andrievskii, D. S.; Barsov, S. G.

2016-12-15

A comparative μSR study of ceramic samples of the EuMn{sub 2}O{sub 5} and Eu{sub 0.8}Ce{sub 0.2}Mn{sub 2}O{sub 5} multiferroics is performed in the temperature range from 15 to 300 K. It is found that the Ce doping of the EuMn{sub 2}O{sub 5} sample slightly reduces the temperature of the magnetic phase transition from T{sub N} = 45 K for the EuMn{sub 2}O{sub 5} sample to T{sub N} = 42.5 K for the Eu{sub 0.8}Ce{sub 0.2}Mn{sub 2}O{sub 5} sample. Below the temperature T{sub N} for both samples, there are two types of localization of a thermalized muon with different temperature dependencesmore » of the precession frequency of the magnetic moment of the muon in an internal magnetic field. The higher frequency in both samples refers to the initial antiferromagnetic matrix. The behavior of this frequency in Eu{sub 0.8}Ce{sub 0.2}Mn{sub 2}O{sub 5} follows the Curie–Weiss law with the exponent β = 0.29 ± 0.02, which differs from the value β = 0.39 standard for 3D Heisenberg magnetics and is observed in EuMn{sub 2}O{sub 5}, because of the strong frustration of the doped sample. The temperature-independent low frequency is due to the presence of Mn{sup 3+}–Mn{sup 4+} ferromagnetic pairs located along the b axis of the antiferromagnetic matrix and in the regions of phase separation, which contain such ion pairs and e{sub g} electrons recharging them. In both samples, polarization losses are the same (about 20%) and are associated with the formation of Mn{sup 4+}–Mn{sup 4+} + Mu complexes near Mn{sup 3+}–Mn{sup 4+} ferromagnetic pairs. In the temperature interval from 25 to 45 K, the separation of the Eu{sub 0.8}Ce{sub 0.2}Mn{sub 2}O{sub 5} structure into two fractions where the relaxation rates of polarization of muons differ by an order of magnitude is revealed. This effect is due to a change in the state of regions of phase separation (1D superlattices) at the indicated temperatures. Such effect in EuMn{sub 2}O{sub 5} is significantly weaker.« less

The optical properties of Sr3SiAl10O20 and Sr3SiAl10O20:Mn4+

NASA Astrophysics Data System (ADS)

Jansen, Thomas; Jüstel, Thomas

2017-11-01

Mn4+-activated luminescent materials have attracted significant attention recently. In particular, alkaline earth aluminates, such as Sr4Al14O25:Mn4+ and CaAl12O19:Mn4+, emit light in the red region, which can be exploited in phosphor-converted LEDs. We applied a sol-gel precursor followed by a ceramic method to synthesize highly crystalline Mn4+-doped Sr3SiAl10O20. The compound Sr3SiAl10O20:Mn4+ exhibits deep red photoluminescence that peaks at 663 nm, which can be assigned to the 2Eg → 4A2g intraconfigurational transition of Mn4+ ([Ar]3d.3 configuration) within the [MnO6]8- octahedra on the aluminum site in the Sr3SiAl10O20 (Space group C12/m1) host structure. The photoluminescence properties, such as the temperature dependence of the luminescence intensity and luminescence lifetime, are presented. Furthermore, the luminescence intensity as function of the activator concentration was investigated. Additionally, the band structure of the undoped host material was treated with Density Functional Theory (DFT). The theoretical results were evaluated experimentally with diffuse UV reflectance spectroscopy. Finally, the crystal field and Racah parameters were extracted to compare with those reported in the literature.

Study of defects and vacancies in structural properties of Mn, co-doped oxides: ZnO

NASA Astrophysics Data System (ADS)

Kumar, Harish; Kaushik, A.; Alvi, P. A.; Dalela, B.; Dalela, S.

2018-05-01

The paper deals with the Structural properties on Mn, Co doped oxides ZnO samples using XRD, Positron Annihilation Lifetime (PAL) Spectra and Raman Spectra. The Mn, Co doped ZnO samples crystallize in a wurtzite structure without any impurity phases in XRD Spectra. The defect state of these samples has been investigated by using positron annihilation lifetime (PAL) spectroscopy technique in which all the relevant lifetime parameters are measured for all the spectra. The results are explained in the direction of doping concentration in these samples in terms of defects structure on Zn lattice site VZn and oxygen defects Vo.

Performance evaluation of Mn and Fe doped SrCo0.9Nb0.1O3-δ cathode for IT-SOFC application

NASA Astrophysics Data System (ADS)

Bele, Lokesh; Lenka, R. K.; Patro, P. K.; Muhmood, L.; Mahata, T.; Sinha, P. K.

2018-02-01

Cathode materials of Mn and Fe doped SrCo0.9Nb0.1O3-δ, are synthesized by solid state route for intermediate temperature fuel cell applications. Phase pure material is obtained after calcining the precursors at 1100 °C. Phase compatibility is observed between this novel cathode material with gadolinia doped ceria (GDC) electrolyte material as reflected in the diffraction pattern. The state of art YSZ electrolyte is not compatible with this cathode material. Average thermal expansion coefficient of the material varies between 17 to 22 X 10-6 K-1 on doping, from room temperature to 800 °C. Increase in thermal expansion coefficient is observed with Mn and Fe doping associated with the loss of oxygen from the crystal. The electrical conductivity of the cathode material decreases with Fe and Mn doping. Mn doped samples show lowest conductivity. From the symmetric cell measurement lower area specific resistance (0.16 Ω-cm2) is obtained for un-doped samples, at 850 °C. From the initial results it can be inferred that Mn/Fe doping improves neither the thermal expansion co-efficient nor the electrochemical activity.

Effect of Cu Doping on the Structural and Electrochemical Performance of LiNi1/3Co1/3Mn1/3O2 Cathode Materials

NASA Astrophysics Data System (ADS)

Yang, Li; Ren, Fengzhagn; Feng, Qigao; Xu, Guangri; Li, Xiaobo; Li, Yuanchao; Zhao, Erqing; Ma, Jignjign; Fan, Shumin

2018-04-01

The structural and electrochemical performance of Cu-doped, Li[Ni1/3-xCo1/3 Mn1/3Cux]O2 (x = 0-0.1) cathode materials obtained by means of the sol-gel method are discussed; we used critic acid as gels and spent mixed batteries as the raw materials. The effects of the sintering time, sintering temperature, and Cu doping ratio on the phase structure, morphology, and element composition and the behavior in a galvanostatical charge/discharge test have been systemically studied. The results show that the Cu-doped material exhibits better galvanostatic charge/discharge cycling performance. At 0.2 C, its original discharge specific capacity is 180.4 mAh g-1 and its Coulomb efficiency is 90.3%. The Cu-doped material demonstrate an outstanding specific capacity at 0.2 C, 0.5 C, and 2.0 C. In comparison with the original capacities of 178 mAh g-1, 159.5 mAh g-1, and 119.4 mAh g-1, the discharge capacity after 50 cycles is 160.8 mAh g-1, 143.4 mAh g-1, and 90.1 mAh g-1, respectively. This obvious improvement relative to bare Li[Ni1/3Co1/3Mn1/3]O2 cathode materials arises from an enlarged Li layer spacing and a reduced degree of cation mixing. Therefore, Cu-doped cathode materials have obvious advantages in the field of lithium-ion batteries and their applications.

Effect of Cu Doping on the Structural and Electrochemical Performance of LiNi1/3Co1/3Mn1/3O2 Cathode Materials

NASA Astrophysics Data System (ADS)

Yang, Li; Ren, Fengzhagn; Feng, Qigao; Xu, Guangri; Li, Xiaobo; Li, Yuanchao; Zhao, Erqing; Ma, Jignjign; Fan, Shumin

2018-07-01

The structural and electrochemical performance of Cu-doped, Li[Ni1/3-xCo1/3 Mn1/3Cux]O2 ( x = 0-0.1) cathode materials obtained by means of the sol-gel method are discussed; we used critic acid as gels and spent mixed batteries as the raw materials. The effects of the sintering time, sintering temperature, and Cu doping ratio on the phase structure, morphology, and element composition and the behavior in a galvanostatical charge/discharge test have been systemically studied. The results show that the Cu-doped material exhibits better galvanostatic charge/discharge cycling performance. At 0.2 C, its original discharge specific capacity is 180.4 mAh g-1 and its Coulomb efficiency is 90.3%. The Cu-doped material demonstrate an outstanding specific capacity at 0.2 C, 0.5 C, and 2.0 C. In comparison with the original capacities of 178 mAh g-1, 159.5 mAh g-1, and 119.4 mAh g-1, the discharge capacity after 50 cycles is 160.8 mAh g-1, 143.4 mAh g-1, and 90.1 mAh g-1, respectively. This obvious improvement relative to bare Li[Ni1/3Co1/3Mn1/3]O2 cathode materials arises from an enlarged Li layer spacing and a reduced degree of cation mixing. Therefore, Cu-doped cathode materials have obvious advantages in the field of lithium-ion batteries and their applications.

Arsenic transformation and adsorption by iron hydroxide/manganese dioxide doped straw activated carbon

NASA Astrophysics Data System (ADS)

Xiong, Ying; Tong, Qiang; Shan, Weijun; Xing, Zhiqiang; Wang, Yuejiao; Wen, Siqi; Lou, Zhenning

2017-09-01

Iron hydroxide/manganese dioxide doped straw activated carbon was synthesized for As(III) adsorption. The Fe-Mn-SAc adsorbent has two advantages, on the one hand, the straw active carbon has a large surface area (1360.99 m2 g-1) for FeOOH and MnO2 deposition, on the other hand, the manganese dioxide has oxidative property as a redox potential of (MnO2 + H+)/Mn2+, which could convert As(III) into As(V). Combined with the arsenic species after reacting with Fe-Mn-SAc, the As(III) transformation and adsorption mechanism was discussed. H2AsO4-oxidized from As(III) reacts with the Fe-Mn-SAc by electrostatic interaction, and unoxidized As(III) as H3AsO3 reacts with SAc and/or iron oxide surface by chelation effect. The adsorption was well-described by Langmuir isotherms model, and the adsorption capacity of As(III) was 75.82 mg g-1 at pH 3. Therefore, considering the straw as waste biomass material, the biosorbent (Fe-Mn-SAc) is promising to be exploited for applications in the treatment of industrial wastewaters containing a certain ratio of arsenic and germanium.

Ferroelectricity-induced resistive switching in Pb(Zr0.52Ti0.48)O3/Pr0.7Ca0.3MnO3/Nb-doped SrTiO3 epitaxial heterostructure

NASA Astrophysics Data System (ADS)

Md. Sadaf, Sharif; Mostafa Bourim, El; Liu, Xinjun; Hasan Choudhury, Sakeb; Kim, Dong-Wook; Hwang, Hyunsang

2012-03-01

We investigated the effect of a ferroelectric Pb(Zr0.52Ti0.48)O3 (PZT) thin film on the generation of resistive switching in a stacked Pr0.7Ca0.3MnO3 (PCMO)/Nb-doped SrTiO3 (Nb:STO) heterostructure forming a p-n junction. To promote the ferroelectric effect, the thin PZT active layer was deposited on an epitaxially grown p-type PCMO film on a lattice-matched n-type Nb:STO single crystal. It was concluded that the observed resistive switching behavior in the all-perovskite Pt/PZT/PCMO/Nb:STO heterostructure was related to the modulation of PCMO/Nb:STO p-n junction's depletion width, which was caused either by the PZT ferroelectric polarization field effect, the electrochemical drift of oxygen ions under an electric field, or both simultaneously.

Development and Properties of Advanced Internal Magnesium Infiltration (AIMI) Processed MgB2 Wires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collings, Prof Edward William; Sumption, Prof Michael D; Li, Guangze

The development, processing, properties, and formation mechanisms of Advanced Internal Magnesium Infiltration (AIMI) MgB2 wires are discussed against a background of the related and original processes, Internal-Magnesium-Diffusion (IMD) and Magnesium-Reactive-Liquid-Infiltration (Mg-RLI). First reviewed are the formation, properties and applications of Mg-RLI bulks as basis for discussions of Mg-RLI-processed and IMD-processed wires. The transition from Mg-RLI- and IMD- to AIMI wires is explained, and the relative performances of powder-in-tube (PIT), IMD and AIMI wires are summarized in the form of an iso-Je diagram of Jc,nb versus Anb/ATOT in which ATOT, Anb, Jc,nb, and Je are, respectively, the wire s cross-sectional area,more » the area inside the chemical barrier, the critical current (Ic) normalized to Anb, and Ic normalized to ATOT. After the details of AIMI wire fabrication selection of starting powders, dopants, and reaction heat treatments are introduced the report goes on to describe in detail the development of high performance AIMI wires: layer Jcs, fill factors, Jes, and the effects of wire size, multifilamentarization, doping with C, and co-doping with C and Dy2O3. The two-stage mechanism of layer formation in AIMI wires is discussed: first the reactive infiltration of liquid Mg into a porous B pack, a process that terminates with the formation of a dense MgB2 layer; second the slow diffusion of Mg into any remaining B through that MgB2 layer. The report concludes with a brief general discussion of anisotropy, current percolation, and the Jc field dependence of MgB2 wires.« less

Luminescence of Mn4+ ions in CaTiO3 and MgTiO3 perovskites: Relationship of experimental spectroscopic data and crystal field calculations

NASA Astrophysics Data System (ADS)

Đorđević, Vesna; Brik, Mikhail G.; Srivastava, Alok M.; Medić, Mina; Vulić, Predrag; Glais, Estelle; Viana, Bruno; Dramićanin, Miroslav D.

2017-12-01

Herein, the synthesis, structural and crystal field analysis and optical spectroscopy of Mn4+ doped metal titanates ATiO3 (A = Ca, Mg) are presented. Materials of desired phase were prepared by molten salt assisted sol-gel method in the powder form. Crystallographic data of samples were obtained by refinement of X-ray diffraction measurements. From experimental excitation and emission spectra and structural data, crystal field parameters and energy levels of Mn4+ in CaTiO3 and MgTiO3 were calculated by the exchange charge model of crystal-field theory. It is found that crystalline field strength is lower (Dq = 1831 cm-1) in the rhombohedral Ilmenite MgTiO3 structure due to the relatively longer average Mn4+sbnd O2- bond distance (2.059 Å), and higher (Dq = 2017 cm-1) in orthorhombic CaTiO3 which possess shorter average Mn4+sbnd O2- bond distance (1.956 Å). Spectral positions of the Mn4+2Eg → 4A2g transition maxima is 709 nm in MgTiO3 and 717 nm in CaTiO3 respectively in good agreement with calculated values.

Enhanced specific heat jump in electron-doped CaMnO3: Spin ordering driven by charge separation

NASA Astrophysics Data System (ADS)

Moritomo, Y.; Machida, A.; Nishibori, E.; Takata, M.; Sakata, M.

2001-12-01

Temperature variation of the magnetic susceptibility χ, resistivity ρ, specific heat C, and lattice constants has been investigated in electron-doped CaMnO3. The parent CaMnO3 is an antiferromagnetic band insulator, and shows an insulator-metal crossover with electron doping, together with an enhanced ferromagnetic component. We have found an enhancement of the specific heat jump ΔC at the spin-ordering temperature Tspin and interpreted the enhancement in terms of the intrinsic charge separation.

Influence of in situ and ex situ ZrO2 addition on the properties of MgB2

NASA Astrophysics Data System (ADS)

Chen, S. K.; Glowacki, B. A.; MacManus-Driscoll, J. L.; Vickers, M. E.; Majoros, M.

2004-02-01

The effect of ZrO2 addition on the properties of MgB2 has been studied using in situ and ex situ processes. The in situ process was performed by introducing ZrO2 from the milling tools into MgB2 throughout the planetary ball milling, whereas the ex situ process was accomplished by mixing ZrO2 from the milling tools with MgB2 by hand grinding in a mortar. A detectable amount of ZrO2 was present in MgB2 after 4 h of milling during the in situ process and its content increased with milling time as expected. The 400 h milled powder was partially amorphized and showed the formation of a minority ZrB2 phase. For milling up to 100 h, diamagnetism of MgB2 was significantly reduced while Tc remained unchanged. Superconductivity was totally destroyed after 148 h of milling. The loss of superconductivity is attributed to the effect of disordering induced by mechanical milling. As a result of in situ ZrO2 addition, the initial Tc and crystal structure of MgB2 could not be restored upon annealing. With increasing milling time, the expansion of lattice parameters in both the a-axis and c-axis may be due to possible substitution of Mg or B by Zr. The result from the magnetic measurement shows that Jc of MgB2 is deteriorated by in situ ZrO2 addition. On the other hand, ex situ ZrO2 addition with annealing did not degrade the Tc of MgB2.

The effect of cobalt doping on the morphology and electrochemical performance of high-voltage spinel LiNi 0.5Mn 1.5O 4 cathode material

DOE PAGES

Mao, Jing; Ma, Mengze; Liu, Panpan; ...

2016-06-03

In this paper, to reveal the effects of Co-doping on the electrochemical performance of micro-sized LiNi 0.5Mn 1.5O 4 (LNMO), undoped LNMO and Co-doped LiCo 0.1Ni 0.45Mn 1.45O 4 (LCoNMO) are synthesized via a PVP-combustion method and calcined at 1000 °C for 6 h. SEM and XRD analyses suggest that Co-doping decreases the particle size and the Li zNi 1-zO 2 impurity at the calcination temperature of 1000 °C. LCoNMO has much better rate capability while its specific capacity at C/5 is 10% lower than that of LNMO. At 15 C rate, their specific capacities are closed, and the LCoNMOmore » delivers 86.2% capacity relative to C/5, and this value for LNMO is only 77.0%. The D Li + values determined by potential intermittent titration technique (PITT) test of LCoNMO are 1–2 times higher than that of LNMO in most SOC region. The LCoNMO shows very excellent cycling performance, which is the best value compared with literatures. After 1000 cycles, the LCoNMO still delivers 94.1% capacity. Finally, moreover, its coulombic efficiency and energy efficiency keep at 99.84% and over 97.3% during 1 C cycling, respectively.« less

The effect of cobalt doping on the morphology and electrochemical performance of high-voltage spinel LiNi 0.5Mn 1.5O 4 cathode material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mao, Jing; Ma, Mengze; Liu, Panpan

In this paper, to reveal the effects of Co-doping on the electrochemical performance of micro-sized LiNi 0.5Mn 1.5O 4 (LNMO), undoped LNMO and Co-doped LiCo 0.1Ni 0.45Mn 1.45O 4 (LCoNMO) are synthesized via a PVP-combustion method and calcined at 1000 °C for 6 h. SEM and XRD analyses suggest that Co-doping decreases the particle size and the Li zNi 1-zO 2 impurity at the calcination temperature of 1000 °C. LCoNMO has much better rate capability while its specific capacity at C/5 is 10% lower than that of LNMO. At 15 C rate, their specific capacities are closed, and the LCoNMOmore » delivers 86.2% capacity relative to C/5, and this value for LNMO is only 77.0%. The D Li + values determined by potential intermittent titration technique (PITT) test of LCoNMO are 1–2 times higher than that of LNMO in most SOC region. The LCoNMO shows very excellent cycling performance, which is the best value compared with literatures. After 1000 cycles, the LCoNMO still delivers 94.1% capacity. Finally, moreover, its coulombic efficiency and energy efficiency keep at 99.84% and over 97.3% during 1 C cycling, respectively.« less

Doping Li-rich cathode material Li2MnO3 : Interplay between lattice site preference, electronic structure, and delithiation mechanism

NASA Astrophysics Data System (ADS)

Hoang, Khang

2017-12-01

We report a detailed first-principles study of doping in Li2MnO3 , in both the dilute doping limit and heavy doping, using hybrid density-functional calculations. We find that Al, Fe, Mo, and Ru impurities are energetically most favorable when incorporated into Li2MnO3 at the Mn site, whereas Mg is most favorable when doped at the Li sites. Nickel, on the other hand, can be incorporated at the Li site and/or the Mn site, and the distribution of Ni over the lattice sites can be tuned by tuning the material preparation conditions. There is a strong interplay among the lattice site preference and charge and spin states of the dopant, the electronic structure of the doped material, and the delithiation mechanism. The calculated electronic structure and voltage profile indicate that in Ni-, Mo-, or Ru-doped Li2MnO3 , oxidation occurs on the electrochemically active transition-metal ion(s) before it does on oxygen during the delithiation process. The role of the dopants is to provide charge compensation and bulk electronic conduction mechanisms in the initial stages of delithiation, hence enabling the oxidation of the lattice oxygen in the later stages. This work thus illustrates how the oxygen-oxidation mechanism can be used in combination with the conventional mechanism involving transition-metal cations in design of high-capacity battery cathode materials.

Magnetic phase change in Mn-doped ZnSnAs2 thin films depending on Mn concentration

NASA Astrophysics Data System (ADS)

Uchitomi, Naotaka; Hidaka, Shiro; Saito, Shin; Asubar, Joel T.; Toyota, Hideyuki

2018-04-01

The relationship between Mn concentration and Curie temperature (TC) is studied for Mn-doped ZnSnAs2 ferromagnetic semiconductors, epitaxially grown on InP substrates by molecular beam epitaxy. In the ferromagnetic phase, Mn distributions in a (Zn,Mn,Sn)As2 thin film with 7.2 cation percent (cat. %) Mn are investigated using three-dimensional atom probe tomography. The results indicate an inhomogeneous distribution which spreads to a relatively high Mn concentration of 9.0 at. % (at. %). In the paramagnetic phase, it is found that the paramagnetic to ferromagnetic transition takes place sharply with a TC of 334 K when the Mn doping concentration increases to about 4 cat. % Mn, which corresponds to a magnetic percolation threshold for ferromagnetism in (Zn,Mn,Sn)As2. An effective Curie temperature ⟨TC⟩ is considered to bridge the Curie temperatures obtained experimentally to those calculated theoretically in inhomogeneous magnetic semiconductors. The behavior of magnetism in Mn-doped ZnSnAs2 can be explained by three different phases within the present framework.

Effect of Nb and F Co-doping on Li1.2Mn0.54Ni0.13Co0.13O2 Cathode Material for High-Performance Lithium-Ion Batteries

PubMed Central

Ming, Lei; Zhang, Bao; Cao, Yang; Zhang, Jia-Feng; Wang, Chun-Hui; Wang, Xiao-Wei; Li, Hui

2018-01-01

The Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x (x = 0, 0.01, 0.03, 0.05) is prepared by traditional solid-phase method, and the Nb and F ions are successfully doped into Mn and O sites of layered materials Li1.2Mn0.54Co0.13Ni0.13O2, respectively. The incorporating Nb ion in Mn site can effectively restrain the migration of transition metal ions during long-term cycling, and keep the stability of the crystal structure. The Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x shows suppressed voltage fade and higher capacity retention of 98.1% after 200 cycles at rate of 1 C. The replacement of O2− by the strongly electronegative F− is beneficial for suppressed the structure change of Li2MnO3 from the eliminating of oxygen in initial charge process. Therefore, the initial coulombic efficiency of doped Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x gets improved, which is higher than that of pure Li1.2Mn0.54Co0.13Ni0.13O2. In addition, the Nb and F co-doping can effectively enhance the transfer of lithium-ion and electrons, and thus improving rate performance. PMID:29675405

1-D and 2-D morphology of metal cation co-doped (Zn, Mn) TiO2 and investigation of their photocatalytic activity

NASA Astrophysics Data System (ADS)

Benjwal, Poonam; De, Bibekananda; Kar, Kamal K.

2018-01-01

Morphology and electronic bandgap of titania (TiO2) are considered to be the primary factors for determining the photocatalytic efficiency, as they determine the number of active sites for the photocatalytic reactions. In the present study, two different morphologies of TiO2 (nanosphere and nanorod) with varying Zn and Mn co-doping were synthesized by solvothermal and hydrothermal methods to examine their photocatalytic efficiency by methylene blue degradation. The co-doped photocatalysts were characterized by XRD, XPS, SEM, TEM, Raman, FTIR and UV-vis DRS. Further, a comparison has been made with co-doped TiO2 nanospheres and TiO2 nanorods, where Zn, Mn co-doped TiO2 nanorods show higher photocatalytic activity compared to nanospheres. This higher photocatalytic activity of co-doped TiO2 is attributed to its polymorphic phases, as they act as heterojunctions for TiO2. Further, being 1-D nanostructure, the TiO2 nanorods exhibit the straight diffusion path for charge carriers, which reduces the recombination possibilities. The obtained results suggest that the photocatalysis efficiency of TiO2 can be significantly enhanced by tailoring the shape and co-doping concentration, which enforce a new concept for developing the new nanostructures of TiO2.

Specific features of the EPR spectra of KTaO3: Mn nanopowders

NASA Astrophysics Data System (ADS)

Golovina, I. S.; Shanina, B. D.; Geifman, I. N.; Andriiko, A. A.; Chernenko, L. V.

2012-03-01

The electron paramagnetic resonance spectra of KTaO3: Mn nanocrystalline powders in the temperature range from 77 to 620 K have been measured and studied for the first time. The change observed in the spectra has been investigated as a function of the doping level. The doping regions in which Mn2+ ions are individual paramagnetic impurities have been established, as well as the regions where the dipole-dipole and exchange interactions of these ions begin to occur. The spin-Hamiltonian constants for the spectrum of non-interacting individual Mn2+ ions have been determined as follows: g = 2.0022, D = 0.0170 cm-1, and A = 85 × 10-4 cm-1. A significant decrease in the axial constant D in the KTaO3: Mn nanopowder, as compared to the single crystal, has been explained by the remoteness of the charge compensator from the paramagnetic ion and by the influence of the surface of the nanoparticle. It has been assumed that the Mn2+ ions are located near the surface and do not penetrate deep into the crystallites.

Mesoporous MnCeO x solid solutions for low temperature and selective oxidation of hydrocarbons

DOE PAGES

Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; ...

2015-10-15

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn 0.5Ce 0.5O x solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn 0.5Ce 0.5O xmore » solid solution with an ultrahigh manganese doping concentration in the CeO 2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn 4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.« less

Effect of manganese doping on remnant polarization and leakage current in (K0.44,Na0.52,Li0.04)(Nb0.84,Ta0.10,Sb0.06)O3 epitaxial thin films on SrTiO3

NASA Astrophysics Data System (ADS)

Abazari, M.; Akdoǧan, E. K.; Safari, A.

2008-05-01

Single phase, epitaxial, ⟨001⟩ oriented, undoped and 1mol% Mn-doped (K0.44,Na0.52,Li0.04)(Nb0.84,Ta0.10,Sb0.06)O3 thin films of 400nm thickness were synthesized on SrRuO3 coated SrTiO3. Such films exhibit well saturated hysteresis loops and have a spontaneous polarization (Ps) of 10μC /cm2, which is a 150% higher over the Ps of the undoped composition. The coercive field of 1mol% Mn doped films is 13kV/cm. Mn-doping results in three orders of magnitude decrease in leakage current above 50kV/cm electric field, which we attribute to the suppression of intrinsic p-type conductivity of undoped films by Mn donors.

Mineralogy and Geochemistry of the Main Glauconite Bed in the Middle Eocene of Texas: Paleoenvironmental Implications for the Verdine Facies

PubMed Central

Harding, Sherie C.; Nash, Barbara P.; Petersen, Erich U.; Ekdale, A. A.; Bradbury, Christopher D.; Dyar, M. Darby

2014-01-01

The Main Glauconite Bed (MGB) is a pelleted greensand located at Stone City Bluff on the south bank of the Brazos River in Burleson County, Texas. It was deposited during the Middle Eocene regional transgression on the Texas Gulf Coastal Plain. Stratigraphically it lies in the upper Stone City Member, Crockett Formation, Claiborne Group. Its mineralogy and geochemistry were examined in detail, and verdine facies minerals, predominantly odinite, were identified. Few glauconitic minerals were found in the green pelleted sediments of the MGB. Without detailed mineralogical work, glaucony facies minerals and verdine facies minerals are easily mistaken for one another. Their distinction has value in assessing paleoenvironments. In this study, several analytical techniques were employed to assess the mineralogy. X-ray diffraction of oriented and un-oriented clay samples indicated a clay mixture dominated by 7 and 14Å diffraction peaks. Unit cell calculations from XRD data for MGB pellets match the odinite-1M data base. Electron microprobe analyses (EMPA) from the average of 31 data points from clay pellets accompanied with Mössbauer analyses were used to calculate the structural formula which is that of odinite: Fe3+ 0.89 Mg0.45 Al0.67 Fe2+ 0.30 Ti0.01 Mn0.01) Σ = 2.33 (Si1.77 Al0.23) O5.00 (OH)4.00. QEMSCAN (Quantitative Evaluation of Minerals by Scanning Electron Microscopy) data provided mineral maps of quantitative proportions of the constituent clays. The verdine facies is a clay mineral facies associated with shallow marine shelf and lagoonal environments at tropical latitudes with iron influx from nearby runoff. Its depositional environment is well documented in modern nearshore locations. Recognition of verdine facies clays as the dominant constituent of the MGB clay pellets, rather than glaucony facies clays, allows for a more precise assessment of paleoenvironmental conditions. PMID:24503875

Laser-induced fluorescence of phosphors for remote cryogenic thermometry

NASA Technical Reports Server (NTRS)

Beshears, D. L.; Capps, G. J.; Cates, M. R.; Simmons, C. M.; Schwenterly, S. W.

1990-01-01

Remote cryogenic temperature measurements can be made by inducing fluorescence in phosphors with temperature-dependent emissions and measuring the emission lifetimes. The thermographic phosphor technique can be used for making precision, noncontact, cryogenic-temperature measurements in electrically hostile environments, such as high dc electric or magnetic fields. The National Aeronautics and Space Administration is interested in using these thermographic phosphors for mapping hot spots on cryogenic tank walls. Europium-doped lanthanum oxysulfide (La2O2S:Eu) and magnesium fluorogermanate doped with manganese (Mg4FGeO6:Mn) are suitable for low-temperature surface thermometry. Several emission lines, excited by a 337-nm ultraviolet laser, provide fluorescence lifetimes having logarithmic dependence with temperature from 4 to above 125 K. A calibration curve for both La2O2S:Eu and Mg4FGeO6:Mn is presented, as well as emission spectra taken at room temperature and 11 K.

Tuning the magnetic phase transition and the magnetocaloric properties of La0.7Ca0.3MnO3 compounds through Sm-doping

NASA Astrophysics Data System (ADS)

Thanh, Tran Dang; Dung, Nguyen Thi; Van Dang, Nguyen; Bau, Le Viet; Piao, Hong-Guang; Phan, The Long; Huyen Yen, Pham Duc; Hau, Kieu Xuan; Kim, Dong-Hyun; Yu, Seong-Cho

2018-05-01

In this work, we point out that the width and the nature of the magnetic phase transition, TC value, and as well as magnetocaloric effect in La0.7-xSmxCa0.3MnO3 compounds can be easily modified through Sm-doped into La-site. With an increasing Sm concentration, a systematic decrease in the magnetization, TC, and magnetic entropy change (ΔSm) are observed. The Arrott-plot proveds that the samples with x = 0 and 0.1 undergoing a first-order phase transition. Meanwhile, sample x = 0.2 undergoes a second-order phase transition, which exhibits a high value of the relative cooling power (81.5 J/kg at ΔH = 10 kOe). An analysis of the critical behavior based on the modified Arrott plots method has been done for sample x = 0.2. The results proved a coexistence of the long- and short-range interactions in La0.5Sm0.2Ca0.3MnO3 compound.

Molecular design of TiO2 for gigantic red shift via sublattice substitution.

PubMed

Shao, Guosheng; Deng, Quanrong; Wan, Lin; Guo, Meilan; Xia, Xiaohong; Gao, Yun

2010-11-01

The effects of 3d transition metal doping in TiO2 phases have been simulated in detail. The results of modelling indicate that Mn has the biggest potential among 3d transition metals, for the reduction of energy gap and the introduction of effective intermediate bands to allow multi-band optical absorption. On the basis of theoretical formulation, we have incorporated considerable amount of Mn in nano-crystalline TiO2 materials. Mn doped samples demonstrate significant red shift in the optical absorption edge, with a secondary absorption edge corresponding to theoretically predicted intermediate bands/states. The gigantic red shift achievable in Mn-doped TiO2 is expected to extend the useful TiO2 functionalities well beyond the UV threshold via the optical absorption of both visible and infrared photon irradiance.

Controlling Blue and Red Light Emissions from Europium (Eu2+)/Manganese (Mn2+)-Codoped Beta-Tricalcium Phosphate [β-Ca3(PO4)2 (TCP)] Phosphors

NASA Astrophysics Data System (ADS)

Van, Hoang Nhu; Hoan, Bui Thi; Nguyen, Khoi Thi; Tam, Phuong Dinh; Huy, Pham Thanh; Pham, Vuong-Hung

2018-03-01

Tunable light emission from europium (Eu2+)/manganese (Mn2+)-codoped beta-tricalcium phosphate [β-Ca3(PO4)2 (TCP)] has been investigated as a function of the Mn2+ and Eu2+ concentrations and annealing temperature. Eu2+/Mn2+-doped TCP phosphor (Eu/Mn-TCP) was synthesized by coprecipitation method followed by thermal annealing at temperature up to 1100°C. The Eu2+/Mn2+-doped TCP particles have diameter of about 1 μm. The light emission from TCP is enhanced in the sample with 7.5 mol.% Mn2+ and 0.3 mol.% Eu2+ annealed in Ar + 5% H2 atmosphere at 1100°C. The blue band at 430 nm is attributed to the 4f 6 5d 1-4f 7 transition of Eu2+. The sharp peak at 660 nm is ascribed to the 4T1-6A1 transition of Mn2+ in TCP. These results suggest codoping of Eu2+/Mn2+ to TCP phosphor to obtain β-Ca3(PO4)2:Eu2+,Mn2+ phosphors with tunable luminescence, having potential applications in agricultural lighting.

Investigation of luminescence from LuAG: Mn4+ for physiological temperature sensing

NASA Astrophysics Data System (ADS)

Li, Fei; Cai, Jiajia; Chi, FengFeng; Chen, Yonghu; Duan, Changkui; Yin, Min

2017-04-01

Optical thermometry based on luminescent materials has garnered much attention due to its many advantages. But higher sensitivity is still expected in physiological temperature range which is of special significance in medicine and biology. For this purpose, quadrivalent manganese doped lutetium aluminum garnet, Lu3Al5O12: Mn4+, or simply LuAG: Mn4+, has been successfully synthesized by sol-gel method and its temperature dependent luminescence has been investigated in the present work. Compared to the common red emission phosphors Y3Al5O12: Mn4+ (YAG:Mn4+) with same structure, LuAG:Mn4+ has a stronger crystal field strength and a higher thermal-quenching activation energy (ΔE) of 5732 cm-1. Rapid thermal quenching of the Mn4+ luminescence occurred above room temperature around 90 °C for our LuAG:Mn4+ sample. Temperature dependent decay curves of Mn4+ emission from LuAG:Mn4+ revealed that an extraordinary high sensitivity can be achieved from luminescence lifetime measurements covering physiological temperature range with a sensitivity of 3.75% K-1 at 38 °C.

Manganese Vanadate Chemistry in Hydrothermal BaF 2 Brines: Ba 3 Mn 2 (V 2 O 7 ) 2 F 2 and Ba 7 Mn 8 O 2 (VO 4 ) 2 F 23

DOE PAGES

Sanjeewa, Liurukara D.; McMillen, Colin D.; McGuire, Michael A.; ...

2016-12-05

We synthesized manganese vanadate fluorides using high-temperature hydrothermal techniques with BaF 2 as a mineralizer. Ba 3Mn 2(V 2O 7) 2F 2 crystallizes in space group C2/c and consists of dimers built from edge-sharing MnO 4F 2 trigonal prisms with linking V 2O 7 groups. Ba 7Mn 8O 2(VO 4) 2F 23 crystallizes in space group Cmmm, with a manganese oxyfluoride network built from edge- and corner-sharing Mn 2+/3+(O,F) 6 octahedra. The resulting octahedra form alternating Mn 2+ and Mn 2+/3+ layers separated by VO 4 tetrahedra. This latter compound exhibits a canted antiferromagnetic order below TN = 25 K.

Internal friction in particulate composites of (x)Mn0.4Zn0.6Fe2O4 –(1-x)PbZr0.53Ti0.47O3 in the vicinity of the structural phase transition temperatures

NASA Astrophysics Data System (ADS)

Kalgin, A. V.; Gridnev, S. A.

2018-03-01

The internal friction in particulate ceramic composites of (x)Mn0.4Zn0.6Fe2O4 –(1-x)PbZr0.53Ti0.47O3 (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.6) in the vicinity of the phase transition temperatures was studied. We observed the influence of the composite composition on the exponent that characterizes a temperature dependence of the internal friction near the ferroelectric Curie point. The reason for this influence is shown to be the doping of the PbZr0.53Ti0.47O3 ferroelectric phase with atoms of the Mn04Zn0.6Fe2O4 ferrite phase that occurs during high- temperature sintering of composite samples.

Oriented Attachment Is a Major Control Mechanism To Form Nail-like Mn-Doped ZnO Nanocrystals.

PubMed

Patterson, Samuel; Arora, Priyanka; Price, Paige; Dittmar, Jasper W; Das, Vijay Kumar; Pink, Maren; Stein, Barry; Morgan, David Gene; Losovyj, Yaroslav; Koczkur, Kallum M; Skrabalak, Sara E; Bronstein, Lyudmila M

2017-12-26

Here, we present a controlled synthesis of Mn-doped ZnO nanoparticles (NPs) with predominantly nail-like shapes, whose formation occurs via tip-to-base-oriented attachment of initially formed nanopyramids, followed by leveling of sharp edges that lead to smooth single-crystalline "nails". This shape is prevalent in noncoordinating solvents such as octadecene and octadecane. Yet, the double bond in the former promotes oriented attachment. By contrast, Mn-doped ZnO NP synthesis in a weakly coordinating solvent, benzyl ether, results in dendritic structures because of random attachment of initial NPs. Mn-doped ZnO NPs possess a hexagonal wurtzite structure, and in the majority of cases, the NP surface is enriched with Mn, indicating a migration of Mn 2+ ions to the NP surface during the NP formation. When the NP formation is carried out without the addition of octadecyl alcohol, which serves as a surfactant and a reaction initiator, large, concave pyramid dimers are formed whose attachment takes place via basal planes. UV-vis and photoluminescence spectra of these NPs confirm the utility of controlling the NP shape to tune electro-optical properties.

Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.

2016-09-15

Large single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO{sub 4}F{sub 2} building blocks. The A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains ofmore » edge-sharing MnO{sub 4}F{sub 2} units running along the a-axis, and interconnected through V{sub 2}O{sub 7} pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn{sup 2+} indicated that Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} is antiferromagnetic with a Neél temperature, T{sub N}=~3 K and a Weiss constant, θ, of −11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}. Mn{sub 2}(VO{sub 4})F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn{sup 2+}. These interpenetrating chains are additionally connected through isolated VO{sub 4} tetrahedra to form the condensed structure. - Graphical abstract: New vanadate fluorides A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}(VO{sub 4})F have been synthesized hydrothermally. Upon cooling, the one-dimensional Mn(II) substructure results in antiferromagnetic ordering. Display Omitted - Highlights: • Single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}, (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown hydrothermally. • The use of fluoride mineralizers in the synthesis led to the formation of new compounds without OH{sup −} groups. • The structure of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} features zigzag chains of MnO{sub 4}F{sub 2} units. • Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} exhibits antiferromagnetic ordering with a Neel temperature of ~3 K. • Mn{sub 2}VO{sub 4}F possesses a condensed framework structure with disordered fluorine atoms.« less

Synthesis, self-assembly, and properties of Mn doped ZnO nanoparticles.

PubMed

Barick, K C; Bahadur, D

2007-06-01

We report here a novel process to prepare Mn doped ZnO nanoparticles by a soft chemical route at low temperature. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and manganese acetate tetrahydrate heated under reflux to 160-175 degrees C using diethylene glycol as a solvent. X-ray diffraction analysis reveals that the Mn doped ZnO crystallizes in a wurtzite structure with crystal size of 15-25 nm. These nano size crystallites of Mn doped ZnO self-organize into polydisperse spheres in size ranging from 100-400 nm. Transmission Electron Microscopy image also shows that each sphere is made up of numerous nanocrystals of average diameter 15-25 nm. By means of X-ray photoelectron spectroscopy and electron spin resonance spectroscopy, we determined the valence state of Mn ions as 2+. These nanoparticles were found to be ferromagnetic at room temperature. Monodisperse porous spheres (approximately 250 nm) were obtained by size selective separation technique and then self-assembled in a closed pack periodic array through sedimentation with slow solvent evaporation, which gives strong opalescence in visible region.

Microstructural, Magnetic, and Optical Properties of Pr-Doped Perovskite Manganite La0.67Ca0.33MnO3 Nanoparticles Synthesized via Sol-Gel Process

NASA Astrophysics Data System (ADS)

Xia, Weiren; Wu, Heng; Xue, Piaojie; Zhu, Xinhua

2018-05-01

We report on microstructural, magnetic, and optical properties of Pr-doped perovskite manganite (La1 - xPrx)0.67Ca0.33MnO3 (LPCMO, x = 0.0-0.5) nanoparticles synthesized via sol-gel process. Structural characterizations (X-ray and electron diffraction patterns, (high resolution) TEM images) provide information regarding the phase formation and the single-crystalline nature of the LPCMO systems. X-ray and electron diffraction patterns reveal that all the LPCMO samples crystallize in perovskite crystallography with an orthorhombic structure ( Pnma space group), where the MnO6 octahedron is elongated along the b axis due to the Jahn-Teller effect. That is confirmed by Raman spectra. Crystallite sizes and grain sizes were calculated from XRD and TEM respectively, and the lattice fringes resolved in the high-resolution TEM images of individual LPCMO nanoparticle confirmed its single-crystalline nature. FTIR spectra identify the characteristic Mn-O bond stretching vibration mode near 600 cm- 1, which shifts towards high wavenumbers with increasing post-annealing temperature or Pr-doping concentration, resulting in further distortion of the MnO6 octahedron. XPS revealed dual oxidation states of Mn3+ and Mn4+ in the LPCMO nanoparticles. UV-vis absorption spectra confirm the semiconducting nature of the LPCMO nanoparticles with optical bandgaps of 2.55-2.71 eV. Magnetic measurements as a function of temperature and magnetic field at field cooling and zero-field cooling modes, provided a Curie temperature around 230 K, saturation magnetization of about 81 emu/g, and coercive field of 390 Oe at 10 K. Such magnetic properties and the semiconducting nature of the LPCMO nanoparticles will make them as suitable candidate for magnetic semiconductor spintronics.

Mitigation of chromium poisoning of cathodes in solid oxide fuel cells employing CuMn1.8O4 spinel coating on metallic interconnect

NASA Astrophysics Data System (ADS)

Wang, Ruofan; Sun, Zhihao; Pal, Uday B.; Gopalan, Srikanth; Basu, Soumendra N.

2018-02-01

Chromium poisoning is one of the major reasons for cathode performance degradation in solid oxide fuel cells (SOFCs). To mitigate the effect of Cr-poisoning, a protective coating on the surface of interconnect for suppressing Cr vaporization is necessary. Among the various coating materials, Cu-Mn spinel coating is considered to be a potential candidate due to their good thermal compatibility, high stability and good electronic conductivity at high temperature. In this study, Crofer 22 H meshes with no protective coating, those with commercial CuMn2O4 spinel coating and the ones with lab-developed CuMn1.8O4 spinel coating were investigated. The lab-developed CuMn1.8O4 spinel coating were deposited on Crofer 22 H mesh by electrophoretic deposition and densified by a reduction and re-oxidation process. With these different Crofer 22 H meshes (bare, CuMn2O4-coated, and CuMn1.8O4-coated), anode-supported SOFCs with Sr-doped LaMnO3-based cathode were electrochemically tested at 800 °C for total durations of up to 288 h. Comparing the mitigating effects of the two types of Cu-Mn spinel coatings on Cr-poisoning, it was found that the performance of the denser lab-developed CuMn1.8O4 spinel coating was distinctly better, showing no degradation in the cell electrochemical performance and significantly less Cr deposition near the cathode/electrolyte interface after the test.

The effect of doping (Mn,B)3O4 materials as protective layers in different metallic interconnects for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Miguel-Pérez, Verónica; Martínez-Amesti, Ana; Nó, María Luisa; Larrañaga, Aitor; Arriortua, María Isabel

2013-12-01

Spinel oxides with the general formula of (Mn,B)3O4 (B = Co, Fe) were used as barrier materials between the cathode and the metallic interconnect to reduce the rate of cathode degradation by Cr poisoning. The effect of doping at the B position was investigated terms of microstructure and electrical conductivity to determine its behaviour and effectiveness as a protective layer in contact with three metallic materials (Crofer 22 APU, SS430 and Conicro 4023 W 188). The analysis showed that the use of these materials considerably decreased the reactivity and diffusion of Cr between the cathode and the metallic interconnects. The protective layer doped with Fe at the B position exhibited the least amount of reactivity with the interconnector and cathode materials. The worst results were observed for SS430 cells coated with a protective layer perhaps due to their low Cr content. The Crofer 22 APU and Conicro 4023 W 188 samples exhibited very similar conductivity results in the presence of the MnCo1.9Fe0.1O4 protective coating. As a result, these two material combinations are a promising option for use as bipolar plates in SOFC.

On the state of Mn in Mn{sub x}Zn{sub 1−x}O nanoparticles and their surface modification with isonipecotic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiménez-Hernández, L.; Estévez-Hernández, O.; Instituto de Ciencia y Tecnología de Materiales

Mn-doped ZnO (Mn{sub x}Zn{sub 1−x}O) nanoparticles were synthesized by the co-precipitation method and coated with isonipecotic acid as capping ligand. The structure, composition and morphology of the resulting nanomaterial were investigated by energy disperse X-ray analysis, X-ray diffraction, and transmission electron microscopy data. Such measurements showed that the solid obtained contains 6 at% of Mn and it is formed by a highly crystalline material with 3–5 nm range of crystallite size, and only a small elongation of its cell parameter with respect to undoped ZnO wurtzite unit cell. Information on the state of manganese atom in the Mn{sub x}Zn{sub 1−x}Omore » nanostructures formed was obtained from X-ray photoelectron (XPS) and electron energy loss (EELS) spectroscopies. XPS and EELS spectra are composed of four peaks, corresponding to two species of Mn(II) and signals from Mn(III) and Mn(IV). Such spectral data on the state of Mn in the material studied is consistent with the mapping of Mn distribution observed in recorded transmission electron microscopy images, which reveal presence of clusters of Mn atoms. Only a fraction of doping Mn atoms were found forming a solid solution with the host ZnO structure. The functionalization of the nanoparticles system with Isonipecotic acid shows that this molecule remains anchored to the nanoparticles surface mainly through its N basic site. The availability of free carboxylate groups in the capping molecule was tested by conjugation to type IV horseradish peroxidase. - Graphical abstract: State of Mn atoms in Mn-doped ZnO nanostructures prepared by the precipitation method, their capping with isonipecotic acid and subsequent conjugation to peroxidase. - Highlights: • State of manganese in manganese-doped zinc oxide nanoparticles. • Isonipecotic acid as surface modifier of ZnO nanoparticles. • Peroxidase conjugation to ZnO nanoparticles modified with isonipecotic acid.« less

Infrared photorefractive effect in doped KNbO3 crystals

NASA Astrophysics Data System (ADS)

Medrano, C.; Zgonik, M.; Liakatas, I.; Günter, P.

1996-11-01

The photorefractive sensitivity of potassium niobate crystals doped with Ce, Co, Cu, Fe, Mn, Ni, and Rh and double-doped with Mn and Rh is investigated over an extended spectral range. We present experimental evidence on extrinsic properties important for the photorefractive effect, such as absorption and effective trap density. Photorefractive gratings are investigated with two-wave mixing experiments. Results on exponential gain, response time, and photorefractive sensitivity at near-infrared wavelengths are reported. The best photorefractive sensitivities at 860 and 1064 nm were obtained in crystals doped with Rh, Fe, Mn, and Mn-Rh. This makes them suitable for applications at laser-diode wavelengths; at 1064 nm, however, Rh:KNbO3 shows a better photorefractive sensitivity than the others. .

Improving the Kinetics and Thermodynamics of Mg(BH 4) 2 for Hydrogen Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wood, Brandon; Klebanoff, Lennie; Stavila, Vitalie

The objective of this project is to (1) combine theory, synthesis, and characterization across multiple scales to understand the intrinsic kinetic and thermodynamic limitations in MgB 2/Mg(BH 4) 2; (2) construct and apply a flexible, validated, multiscale theoretical framework for modeling (de)hydrogenation kinetics of the Mg-B-H system and related metal hydrides; and (3) devise strategies for improving kinetics and thermodynamics, particularly through nanostructuring and doping. The project has an emphasis on understanding and improving rehydrogenation of MgB 2, which has generally been less explored and is key to enabling practical use.

Effects of Mn substitution on the thermoelectric properties of the electron-doped perovskite Sr1-xLaxTiO3

NASA Astrophysics Data System (ADS)

Okuda, T.; Hata, H.; Eto, T.; Nishina, K.; Kuwahara, H.; Nakamura, M.; Kajimoto, R.

2014-12-01

We have tried to improve the n-type thermoelectric properties of the electron- doped Perovskite Sr1-xLaxTiO3 by a Mn substitution. The 1 ~ 2 % Mn substitution enhances the Seebeck coefficient (S) and reduces the thermal conductivity (κ) by about 50 % at room temperature (RT) without largely increasing the resistivity for the 5 % electron-doped SrTiO3. Consequently, the power factor at RT keeps a large value comparable to that of Bi2Te3 and the dimensionless figure-of-merits at RT increases twofold by the slight Mn substitution. Such a large reduction of κ at RT is perhaps due to the effect of Jahn-Teller active Mn3+ ions, around which dynamical local lattice distortion may occur.

Electronic and magnetic ordering induced by Mo- and Ru doping of the Mn site in CaMnO3 perovskite: EMR probing

NASA Astrophysics Data System (ADS)

Shames, A. I.; Auslender, M.; Rozenberg, E.; Gorodetsky, G.; Martin, C.; Maignan, A.

2005-05-01

X-band electron magnetic-resonance (EMR) measurements of polycrystalline CaMn1-yMoyO3 (0⩽y ⩽0.14) samples were performed at 120K⩽T⩽540K. The data obtained are compared with those of another electron-doped manganite system, CaMn1-xRuxO3 (0⩽x ⩽0.40). The observed anomalies of the EMR parameters correlate pretty well with the temperatures of antiferro-, ferromagneticlike, and orbital/charge-ordering transitions in these systems. However, a strong difference is observed between the resonant properties of Mo- and Ru doped series at both paramagnetic (PM) and magnetically ordered states. To describe such a difference, the energy-band diagrams, which comprise the deep impurity t2g-like states +eg-like conductive band for CaMn1-xRuxO3 and shallow impurity states+conductive band, both having eg-like symmetry, for CaMn1-yMoyO3, are proposed. Specific electrons' contribution to the EMR linewidth at PM temperatures is introduced for the considered systems.

The Effect of Remelting on the Physical Properties of Borotellurite Glass Doped with Manganese

PubMed Central

Hashim, Syed Putra Hashim Syed; Sidek, Haji Abdul Aziz; Halimah, Mohamed Kamari; Matori, Khamirul Amin; Yusof, Wan Mohamad Daud Wan; Zaid, Mohd Hafiz Mohd

2013-01-01

A systematic set of borotellurite glasses doped with manganese (1–x) [(B2O3)0.3(TeO2)0.7]-xMnO, with x = 0.1, 0.2, 0.3 and 0.4 mol%, were successfully synthesized by using a conventional melt and quench-casting technique. In this study, the remelting effect of the glass samples on their microstructure was investigated through density measurement and FT-IR spectra and evaluated by XRD techniques. Initial experimental results from XRD evaluation show that there are two distinct phases of glassy and crystallite microstructure due to the existence of peaks in the sample. The different physical behaviors of the studied glasses were closely related to the concentration of manganese in each phase. FTIR spectra revealed that the addition of manganese oxide contributes the transformation of TeO4 trigonal bipyramids with bridging oxygen (BO) to TeO3 trigonal pyramids with non-bridging oxygen (NBO). PMID:23296276

Activated carbon doped with biogenic manganese oxides for the removal of indigo carmine.

PubMed

Hu, Yichen; Chen, Xiao; Liu, Zhiqiang; Wang, Gejiao; Liao, Shuijiao

2016-01-15

Indigo carmine (IC) is one of the oldest, most important, and highly toxic dyes which is released from the effluents of many industries and results in serious pollution in water. In this study, the biogenic Mn oxides were activated by NaOH and then heated for 3 h at 350 °C to produce activated carbon doped with Mn oxide (Bio-MnOx-C), which were produced by culturing Mn (II)-oxidizing bacterial strain MnI7-9 in liquid A medium at 28 °C with 10 mmol/L MnCl2. Bio-MnOx-C was characterized by SEM, TEM, IR, XPS, XRD, etc. It contained C, O, and Mn which comprised Mn (IV) and Mn (III) valence states at a ratio of 3.81:1. It had poorly crystalline ε-MnO2 with a specific surface area of 130.94 m(2)/g. A total of 0.1 g Bio-MnOx-C could remove 45.95 g IC from 500 mg/L IC solution after 0.5 h contact time. IC removal by Bio-MnOx-C included a rapid oxidation reaction and the removal reaction followed second-order kinetic equation. These results confirmed that Bio-MnOx-C could be a potential material for wastewater remediation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Double perovskite Ca2GdNbO6:Mn4+ deep red phosphor: Potential application for warm W-LEDs

NASA Astrophysics Data System (ADS)

Lu, Zuizhi; Huang, Tianjiao; Deng, Ruopeng; Wang, Huan; Wen, Lingling; Huang, Meixin; Zhou, Liya; Yao, Chunying

2018-05-01

A novel Mn4+-doped Ca2GdNbO6 (CGN) phosphor was prepared by high-temperature solid-state reaction. The crystal structure was investigated by X-ray diffraction patterns and unit cell structure. Mn4+ replaced the location of Nb5+ in the CGN lattice, and the value of energy gap (Egap) decreased from 2.16 eV to 1.13 eV, indicating that Mn4+ ions play a great influence on the absorption of CGN hosts. The broad excitation band from 250 nm to 550 nm matches well with commercial near-UV light emitting diodes, and the emission peak centered at 680 nm is due to 2E→4A2g transition in Mn4+ ions. The CIE chromaticity coordinates (0.698, 0.303) of CGN:Mn4+ phosphor was close to standard red color coordinates (0.666, 0.333). These investigations demonstrate CGN:Mn4+ phosphor as an efficient red phosphor for potential applications.

Leakage current behavior in lead-free ferroelectric (K,Na)NbO3-LiTaO3-LiSbO3 thin films

NASA Astrophysics Data System (ADS)

Abazari, M.; Safari, A.

2010-12-01

Conduction mechanisms in epitaxial (001)-oriented pure and 1 mol % Mn-doped (K0.44,Na0.52,Li0.04)(Nb0.84,Ta0.1,Sb0.06)O3 (KNN-LT-LS) thin films on SrTiO3 substrate were investigated. Temperature dependence of leakage current density was measured as a function of applied electric field in the range of 200-380 K. It was shown that the different transport mechanisms dominate in pure and Mn-doped thin films. In pure (KNN-LT-LS) thin films, Poole-Frenkel emission was found to be responsible for the leakage, while Schottky emission was the dominant mechanism in Mn-doped thin films at higher electric fields. This is a remarkable yet clear indication of effect of 1 mol % Mn on the resistive behavior of such thin films.

Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F

NASA Astrophysics Data System (ADS)

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.; McMillen, Colin D.; Ovidiu Garlea, V.; Willett, Daniel; Chumanov, George; Kolis, Joseph W.

2016-09-01

Large single crystals of A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO4F2 building blocks. The A2Mn2V2O7F2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb2Mn2V2O7F2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs2Mn2V2O7F2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains of edge-sharing MnO4F2 units running along the a-axis, and interconnected through V2O7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn2+ indicated that Cs2Mn2V2O7F2 is antiferromagnetic with a Neél temperature, TN=~3 K and a Weiss constant, θ, of -11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V-O vibrational modes in Cs2Mn2V2O7F2. Mn2(VO4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn2+. These interpenetrating chains are additionally connected through isolated VO4 tetrahedra to form the condensed structure.

Synthesis and characterization of new fluoride-containing manganese vanadates A 2Mn 2V 2O 7F 2 (A=Rb, Cs) and Mn 2VO 4F

DOE PAGES

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.; ...

2016-05-10

In large single crystals of A 2Mn 2V 2O 7F 2 (A=Rb, Cs) and Mn 2VO 4F were grown using a high-temperature (~600 °C) hydrothermal technique. We utilized single crystal X-ray diffraction and powder X-ray diffraction in order to characterize the structures, which both possess MnO 4F 2 building blocks. The A 2Mn 2V 2O 7F 2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb 2Mn 2V 2O 7F 2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs 2Mn 2V 2O 7F 2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed ofmore » zigzag chains of edge-sharing MnO 4F 2 units running along the a-axis, and interconnected through V 2O 7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn 2+ indicated that Cs 2Mn 2V 2O 7F 2 is antiferromagnetic with a Neél temperature, TN=~3 K and a Weiss constant, θ, of -11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs 2Mn 2V 2O 7F 2. Mn 2(VO 4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn 2+. Our interpenetrating chains are additionally connected through isolated VO 4 tetrahedra to form the condensed structure.« less

EPR and Structural Characterization of Water-Soluble Mn2+-Doped Si Nanoparticles

PubMed Central

2016-01-01

Water-soluble poly(allylamine) Mn2+-doped Si (SiMn) nanoparticles (NPs) were prepared and show promise for biologically related applications. The nanoparticles show both strong photoluminescence and good magnetic resonance contrast imaging. The morphology and average diameter were obtained through transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM); spherical crystalline Si NPs with an average diameter of 4.2 ± 0.7 nm were observed. The doping maximum obtained through this process was an average concentration of 0.4 ± 0.3% Mn per mole of Si. The water-soluble SiMn NPs showed a strong photoluminescence with a quantum yield up to 13%. The SiMn NPs had significant T1 contrast with an r1 relaxivity of 11.1 ± 1.5 mM–1 s–1 and r2 relaxivity of 32.7 ± 4.7 mM–1 s–1 where the concentration is in mM of Mn2+. Dextran-coated poly(allylamine) SiMn NPs produced NPs with T1 and T2 contrast with a r1 relaxivity of 27.1 ± 2.8 mM–1 s–1 and r2 relaxivity of 1078.5 ± 1.9 mM–1 s–1. X-band electron paramagnetic resonance spectra are fit with a two-site model demonstrating that there are two types of Mn2+ in these NP’s. The fits yield hyperfine splittings (A) of 265 and 238 MHz with significant zero field splitting (D and E terms). This is consistent with Mn in sites of symmetry lower than tetrahedral due to the small size of the NP’s. PMID:28154618

Pinning in high performance MgB2 thin films and bulks: Role of Mg-B-O nano-scale inhomogeneities

NASA Astrophysics Data System (ADS)

Prikhna, Tatiana; Shapovalov, Andrey; Eisterer, Michael; Shaternik, Vladimir; Goldacker, Wilfried; Weber, Harald W.; Moshchil, Viktor; Kozyrev, Artem; Sverdun, Vladimir; Boutko, Viktor; Grechnev, Gennadiy; Gusev, Alexandr; Kovylaev, Valeriy; Shaternik, Anton

2017-02-01

The comparison of nano-crystalline MgB2 oxygen-containing thin film (140 nm) and highly dense bulk materials showed that the critical current density, Jc, depends on the distribution of Mg-B-O nano-scale inhomogeneities. It has been shown that MgB2 bulks with high Jc in low (∼106 A/cm2 in 0-1 T at 10 K) and medium magnetic fields contain MgB0.6-0.8O0.8-0.9 nano-inclusions, where δTc or a combined δTc (dominant) / δl pinning mechanism prevails, while in bulk MgB2 with high Jc in high magnetic fields (Birr(18.5 K) = 15 T, Bc2(0 K) = 42.1 T) MgB1.2-2.7O1.8-2.5 nano-layers are present and δl pinning prevails. The structure of oxygen-containing films with high Jc in low and high magnetic fields (Jc (0 Т) = 1.8 × 107 А/сm2 and Jc (5 Т) = 2 × 106 А/сm2 at 10 К) contains very fine oxygen-enriched Mg-B-O inhomogeneities and δl pinning is realized. The results of DOS calculations in MgB2-xOx cells for x = 0, 0.125, 0.25, 0.5, 1 demonstrate that all compounds are conductors with metal-like behaviour. In the case of ordered oxygen substitution for boron the binding energy, Eb, does not increase sufficiently as compared with that for MgB2, while when oxygen atoms form zigzag chains the calculated Eb is even lower (Eb = -1.15712 Ry).

Study of magnetic and electrical properties of nanocrystalline Mn doped NiO.

PubMed

Raja, S Philip; Venkateswaran, C

2011-03-01

Diluted Magnetic Semiconductors (DMS) are intensively explored in recent years for its applications in spintronics, which is expected to revolutionize the present day information technology. Nanocrystalline Mn doped NiO samples were prepared using chemical co-precipitation method with an aim to realize room temperature ferromagnetism. Phase formation of the samples was studied using X-ray diffraction-Rietveld analysis. Scanning electron microscopy and Energy dispersive X-ray analysis results reveal the nanocrystalline nature of the samples, agglomeration of the particles, considerable particle size distribution and the near stoichiometry. Thermomagnetic curves confirm the single-phase formation of the samples up to 1% doping of Mn. Vibrating Sample Magnetometer measurements indicate the absence of ferromagnetism at room temperature. This may be due to the low concentration of Mn2+ ions having weak indirect coupling with Ni2+ ions. The lack of free carriers is also expected to be the reason for the absence of ferromagnetism, which is in agreement with the results of resistivity measurements using impedance spectroscopy. Arrhenius plot shows the presence of two thermally activated regions and the activation energy for the nanocrystalline Mn doped sample was found to be greater than that of undoped NiO. This is attributed to the doping effect of Mn. However, the dielectric constant of the samples was found to be of the same order of magnitude very much comparable with that of undoped NiO.

Switchable Schottky diode characteristics induced by electroforming process in Mn-doped ZnO thin films

NASA Astrophysics Data System (ADS)

Nam, Yoonseung; Hwang, Inrok; Oh, Sungtaek; Lee, Sangik; Lee, Keundong; Hong, Sahwan; Kim, Jinsoo; Choi, Taekjib; Ho Park, Bae

2013-04-01

We investigated the asymmetric current-voltage (I-V) characteristics and accompanying unipolar resistive switching of pure ZnO and Mn(1%)-doped ZnO (Mn:ZnO) films sandwiched between Pt electrodes. After electroforming, a high resistance state of the Mn:ZnO capacitor revealed switchable diode characteristics whose forward direction was determined by the polarity of the electroforming voltage. Linear fitting of the I-V curves highlighted that the rectifying behavior was influenced by a Schottky barrier at the Pt/Mn:ZnO interface. Our results suggest that formation of conducting filaments from the cathode during the electroforming process resulted in a collapse of the Schottky barrier (near the cathode), and rectifying behaviors dominated by a remnant Schottky barrier near the anode.

Chemical disorder influence on magnetic state of optimally-doped La0.7Ca0.3MnO3

NASA Astrophysics Data System (ADS)

Rozenberg, E.; Auslender, M.; Shames, A. I.; Jung, G.; Felner, I.; Tsindlekht, M. I.; Mogilyansky, D.; Sominski, E.; Gedanken, A.; Mukovskii, Ya. M.; Gorodetsky, G.

2011-10-01

X-band electron magnetic resonance and dc/ac magnetic measurements have been employed to study the effects of chemical disorder on magnetic ordering in bulk and nanometer-sized single crystals and bulk ceramics of optimally-doped La0.7Ca0.3MnO3 manganite. The magnetic ground state of bulk samples appeared to be ferromagnetic with the lower Curie temperature and higher magnetic homogeneity in the vicinity of the ferromagnetic-paramagnetic phase transition in the crystal, as compared with those characteristics in the ceramics. The influence of technological driven "macroscopic" fluctuations of Ca-dopant level in crystal and "mesoscopic" disorder within grain boundary regions in ceramics was proposed to be responsible for these effects. Surface spin disorder together with pronounced inter-particle interactions within agglomerated nano-sample results in well defined core/shell spin configuration in La0.7Ca0.3MnO3 nano-crystals. The analysis of the electron paramagnetic resonance data enlightened the reasons for the observed difference in the magnetic order. Lattice effects dominate the first-order nature of magnetic phase transition in bulk samples. However, mesoscale chemical disorder seems to be responsible for the appearance of small ferromagnetic polarons in the paramagnetic state of bulk ceramics. The experimental results and their analysis indicate that a chemical/magnetic disorder has a strong impact on the magnetic state even in the case of mostly stable optimally hole-doped manganites.

Synthesis of K2SiF6:Mn4+ phosphor for LED lamp

NASA Astrophysics Data System (ADS)

Takarkhede, M. G.; Patil, R. R.; Moharil, S. V.; Joshi, C. P.; Talewar, Rupesh

2018-05-01

Now a days red emitting Mn4+ activated dialkali fluorosilicate phosphors have found applications in solid state lighting and displays. In this paper we describe development of K2SiF6 phosphor doped with Mn synthesized by simple method using Si metal powder with addition of oxidizing agent KMnO4. The photoluminescence spectra of K2SiF6:Mn show that emission is in the red region. In addition to this we studied LED spectra by coating the LED with phosphor mixed in different proportions with epoxy.

Effect of Sr-doping on electronic and magnetic properties of La2-xSrxCoMnO6

NASA Astrophysics Data System (ADS)

Khan, Anasua; Chatterjee, Swastika; Mandal, P. R.; Nath, T. K.

2018-04-01

In this report, La2-xSrxCoMnO6 (x=0, 1) have been synthesised using sol-gel technique. La2CoMnO6 (LCMO) takes a monoclinic phase, whereas LaSrCoMnO6 (LSCMO) appears in a mixed phase of having both monoclinic and rhombohedral symmetries. DC magnetization measurement shows that LCMO is Ferromagnetic in nature whereas LSCMO shows magnetic glassy nature. This experimental result is verified by ab-initio calculation using GGA+SO+U as implemented in WIEN2k code. Total energy calculations suggest that antisite disorder is enhanced with Sr doping at La site and LSCMO is predominantly ferromagnetic in nature. Co ions which appeared in high spin +2 charge state, converts to intermediate spin +3 charge state with Sr doping.

Magnetic and Magnetocaloric Properties of Ca0.97La0.03MnO3 Manganites

NASA Astrophysics Data System (ADS)

Gong, G. D.; Hu, P. F.; Li, Y.; Kim, D. H.; Liu, C. L.; Phan, T. L.; Ho, T. A.; Yu, S. C.; Telegin, A.; Naumov, S. V.

2016-07-01

In spite of many previous studies on electron-doped CaMnO3 perovskite manganites, detailed investigations into the influence of low-doping concentrations on their magnetic and magnetocaloric (MC) properties have not been carried out yet. Additionally, there is still the lack of the comparison between single-crystal (SC) and polycrystalline (PC) materials. Dealing with these problems, we prepared orthorhombic Ca0.97La0.03MnO3 SC and PC samples. Magnetization measurements versus the temperature and magnetic field revealed remarkable differences in the magnetic property, particularly around the antiferromagnetic/ferromagnetic-paramagnetic phase-transition region. The analyses of the magnetization versus magnetic field, M( H), data indicated a weak MC effect with magnetic-entropy changes less than 0.1 J kg-1 K-1 for an applied field interval H = 10 kOe because ferromagnetic interactions between Mn3+ and Mn4+ ions are insignificant. The differences in the magnetic and MC properties of the SC and PC samples are ascribed to the effects of grain boundary, magnetic anisotropy, and nonstoichiometry in oxygen.

CuO, MnO2 and Fe2O3 doped biomass ash as silica source for glass production in Thailand

NASA Astrophysics Data System (ADS)

Srisittipokakun, N.; Ruangtaweep, Y.; Rachniyom, W.; Boonin, K.; Kaewkhao, J.

In this research, glass productions from rice husk ash (RHA) and the effect of BaO, CuO, MnO2 and Fe2O3 on physical and optical properties were investigated. All properties were compared with glass made from SiO2 using same preparations. The results show that a higher density and refractive index of BaO, CuO, MnO2 and Fe2O3 doped in RHA glasses were obtained, compared with SiO2 glasses. The optical spectra show no significant difference between both glasses. The color of CuO glasses show blue from the absorption band near 800 nm (2B1g → 2B2g) due to Cu2+ ion in octahedral coordination with a strong tetragonal distortion. The color of MnO2 glasses shows brown from broad band absorption at around 500 nm. This absorption band is assigned to a single allowed 5Eg → 5T2g transition which arises from the Mn3+ ions (3d4 configuration) in octahedral symmetry. The yellow color derives from F2O3 glass due to the homogeneous distribution of Fe3+ (460 nm) and Fe2+ (1050 nm) ions in the glass matrices. Glass production from RHA is possible and is a new option for recycling waste from biomass power plant systems and air pollution reduction.

Effect of Mn in Li3V2-xMnx(PO4)3 as High Capacity Cathodes for Lithium Batteries.

PubMed

Park, Jae-Sang; Kim, Jongsoon; Park, Woon Bae; Sun, Yang-Kook; Myung, Seung-Taek

2017-11-22

Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0, 0.05) cathode materials, which allow extraction of 3 mol of Li from the formula unit, were investigated to achieve a high energy density utilizing multielectron reactions, activated by the V 3+/5+ redox reaction. Structural investigation demonstrates that V 3+ was replaced by equivalent Mn 3+ , as confirmed by Rietveld refinement of the X-ray diffraction data and X-ray absorption near edge spectroscopy. The substitution simultaneously lowered the band gap energy from 3.4 to 3.2 eV, according to a density functional theory calculation. In addition to the effect of Mn doping, surface carbonization of Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0, 0.05) dramatically increased the electric conductivity up to 10 -3 S cm -1 . As a result, the carbon-coated Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0.05) delivered a high discharge (reduction) capacity of approximately 180 mAh g -1 at a current of 20 mA g -1 (0.1 C rate) with excellent retention, delivering approximately 163 mAh g -1 at the 200th cycle. Even at 50 C (10 A g -1 ), the electrode afforded a discharge capacity of 68 mAh g -1 and delivered approximately 104 mAh g -1 (1 C) at -10 °C with the help of Mn doping and carbon coating. The synergetic effects such as a lowered band gap energy by Mn doping and high electric conductivity associated with carbon coating are responsible for the superior electrode performances, including thermal properties with extremely low exothermic heat generation (<0.4 J g -1 for Li 0.02 V 1.95 Mn 0.05 (PO 4 ) 3 ), which is compatible with the layered high energy density of LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 materials.

Inhibition of unintentional extra carriers by Mn valence change for high insulating devices

PubMed Central

Guo, Daoyou; Li, Peigang; Wu, Zhenping; Cui, Wei; Zhao, Xiaolong; Lei, Ming; Li, Linghong; Tang, Weihua

2016-01-01

For intrinsic oxide semiconductors, oxygen vacancies served as the electron donors have long been, and inevitably still are, attributed as the primary cause of conductivity, making oxide semiconductors seem hard to act as high insulating materials. Meanwhile, the presence of oxygen vacancies often leads to a persistent photoconductivity phenomenon which is not conducive to the practical use in the fast photoelectric response devices. Herein, we propose a possible way to reduce the influence of oxygen vacancies by introducing a valence change doping in the monoclinic β-Ga2O3 epitaxial thin film. The unintentional extra electrons induced by oxygen vacancies can be strongly suppressed by the change valence of the doped Mn ions from +3 to +2. The resistance for the Mn-doped Ga2O3 increases two orders of magnitude in compared with the pure Ga2O3. As a result, photodetector based on Mn-doped Ga2O3 thin films takes on a lower dark current, a higher sensitivity, and a faster photoresponse time, exhibiting a promising candidate using in high performance solar-blind photodetector. The study presents that the intentional doping of Mn may provide a convenient and reliable method of obtaining high insulating thin film in oxide semiconductor for the application of specific device. PMID:27068227

Critical current densities of powder-in-tube MgB2 tapes fabricated with nanometer-size Mg powder

NASA Astrophysics Data System (ADS)

Yamada, H.; Hirakawa, M.; Kumakura, H.; Matsumoto, A.; Kitaguchi, H.

2004-03-01

We fabricated powder-in-tube MgB2/Fe tapes using a powder mixture of nanometer-size Mg and commercial amorphous B and investigated the transport properties. High-purity nanometer-size Mg powder was fabricated by applying the thermal plasma method. 5-10 mol % SiC powder doping was tried to enhance the Jc properties. We found that the use of nanometer-size Mg powder was effective to increase the Jc values. The transport Jc values of the nondoped and 10 mol % SiC-doped tapes prepared with nanometer-size Mg powder reached 90 and 250 A/mm2 at 4.2 K and 10 T, respectively. These values were about five times higher than those of the tapes prepared with commercial Mg powder.

Band edge movement and structural modifications in transition metal doped TiO2 nanocrystals for the application of DSSC

NASA Astrophysics Data System (ADS)

Patle, L. B.; Huse, V. R.; Chaudhari, A. L.

2017-10-01

Nanocrystalline undoped and transition metal ion doped (TM:Cu2+, Mn2+ and Fe3+) TiO2 nanoparticles, with 1 mol% were synthesized by a simple and cost effective modified co-precipitation method at room temperature and were successfully used as photoanode for dye sensitized solar cell (DSSC). The effect of transition metal ions into TiO2 nano crystalline powder has been systematically investigated using x-ray diffraction (XRD), UV-Vis spectroscope, scanning electron microscope (SEM), transmission electron microscope (TEM) and energy dispersive x-ray spectroscopy (EDX). The results of XRD confirm nanocrystalline anatase tetragonal structure of prepared undoped and TM doped TiO2 semiconductor. The influence of doping on band edge movement has been estimated using UV-visible spectroscopy. The SEM results indicate that microscopic effect of doping on morphology of the TiO2. The peaks of EDX signify incorporation of transition metal cations into TiO2 lattice. The effect of doping on flat band potential was estimated using interpolation on Mott-Schottky plot. The performances of DSSCs of undoped and doped TiO2 photoelectrodes were investigated under light illumination. In comparison with undoped and (Cu2+, Fe3+) doped TiO2 photoanodes we found that incorporation of Mn2+ into TiO2 exhibits improvement in photoconversion efficiency (η). There is increase in photoconversion efficiency of DSSCs with Mn2+ doped TiO2 by 6% as compared to that of undoped TiO2 photoanode.

Understanding ferromagnetism and optical absorption in 3d transition metal-doped cubic ZrO{sub 2} with the modified Becke-Johnson exchange-correlation functional

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boujnah, M.; Zaari, H.; El Kenz, A., E-mail: elkenz@fsr.ac.ma

The electronic structure, magnetic, and optical properties in cubic crystalline phase of Zr{sub 1−x}TM{sub x}O{sub 2} (TM = V, Mn, Fe, and Co) at x = 6.25% are studied using density functional theory with the Generalized Gradient Approximation and the modified Becke-Johnson of the exchange-correlation energy and potential. In our calculations, the zirconia is a p-type semiconductor and has a large band gap. We evaluated the possibility of long-range magnetic order for transition metal ions substituting Zr. Our results show that ferromagnetism is the ground state in V, Mn, and Fe-doped ZrO{sub 2} and have a high value of energy in Mn-doped ZrO{sub 2}.more » However, in Co-doped ZrO{sub 2}, antiferromagnetic ordering is more stable than the ferromagnetic one. The exchange interaction mechanism has been discussed to explain the responsible of this stability. Moreover, it has been found that the V, Mn, and Fe transition metals provide half-metallic properties considered to be the leading cause, responsible for ferromagnetism. Furthermore, the optical absorption spectra in the TM -doped cubic ZrO{sub 2} are investigated.« less

Magnetic properties of Mg12O12 nanocage doped with transition metal atoms (Mn, Fe, Co and Ni): DFT study

NASA Astrophysics Data System (ADS)

Javan, Masoud Bezi

2015-07-01

Binding energy of the Mg12O12 nanocage doped with transition metals (TM=Mn, Fe, Co and Ni) in endohedrally, exohedrally and substitutionally forms were studied using density functional theory with the generalized gradient approximation exchange-correlation functional along 6 different paths inside and outside of the Mg12O12 nanocage. The most stable structures were determined with full geometry optimization near the minimum of the binding energy curves of all the examined paths inside and outside of the Mg12O12 nanocage. The results reveal that for all stable structures, the Ni atom has a larger binding energy than the other TM atoms. It is also found that for all complexes additional peaks contributed by TM-3d, 4s and 4p states appear in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) gap of the host MgO cluster. The mid-gap states are mainly due to the hybridization between TM-3d, 4s and 4p orbitals and the cage π orbitals. The magnetic moment of the endohedrally doped TM atoms in the Mg12O12 are preserved to some extent due to the interaction between the TM and Mg12O12 nanocage, in contrast to the completely quenched magnetic moment of the Fe and Ni atoms in the Mg11(TM)O12 complexes. Furthermore, charge population analysis shows that charge transfer occurs from TM atom to the cage for endohedrally and substitutionally doping.

3D hierarchical assembly of ultrathin MnO2 nanoflakes on silicon nanowires for high performance micro-supercapacitors in Li- doped ionic liquid

PubMed Central

Dubal, Deepak P.; Aradilla, David; Bidan, Gérard; Gentile, Pascal; Schubert, Thomas J.S.; Wimberg, Jan; Sadki, Saïd; Gomez-Romero, Pedro

2015-01-01

Building of hierarchical core-shell hetero-structures is currently the subject of intensive research in the electrochemical field owing to its potential for making improved electrodes for high-performance micro-supercapacitors. Here we report a novel architecture design of hierarchical MnO2@silicon nanowires (MnO2@SiNWs) hetero-structures directly supported onto silicon wafer coupled with Li-ion doped 1-Methyl-1-propylpyrrolidinium bis(trifluromethylsulfonyl)imide (PMPyrrBTA) ionic liquids as electrolyte for micro-supercapacitors. A unique 3D mesoporous MnO2@SiNWs in Li-ion doped IL electrolyte can be cycled reversibly across a voltage of 2.2 V and exhibits a high areal capacitance of 13 mFcm−2. The high conductivity of the SiNWs arrays combined with the large surface area of ultrathin MnO2 nanoflakes are responsible for the remarkable performance of these MnO2@SiNWs hetero-structures which exhibit high energy density and excellent cycling stability. This combination of hybrid electrode and hybrid electrolyte opens up a novel avenue to design electrode materials for high-performance micro-supercapacitors. PMID:25985388

Investigation of xFe2O4 (x = Mn, Co) doped hydroxylapatite ferromagnetic biomaterials for the treatment of damaged bone and magnetically targeted drug delivery systems

NASA Astrophysics Data System (ADS)

Anand, Vikas; Singh, K. J.; Kaur, Kulwinder; Bhatia, Gaurav

2016-05-01

Magnetically attracted MnFe2O4 and CoFe2O4 doped hydroxylapatite samples have been prepared by using co-precipitation method in the laboratory. Bioactive nature of samples has been confirmed from XRD spectra. Ferromagnetic behavior of samples has been studied by using vibration sample magnetometer. Human osteoblast cell line MG63 has been used to explore the cell viability of samples. Drug carrier ability of samples has been checked with gentamycin as an antibiotic and results show that samples can be used as excellent drug carriers. Drug loaded samples can be easily targeted to specific area due to their attractive nature towards external magnetic field. Our results indicate that prepared samples possess good bioactive as well as ferromagnetic behavior with drug carrier ability and hence, our samples can be potential candidates for the clinical applications.

Hole transport in pure and doped hematite

NASA Astrophysics Data System (ADS)

Liao, Peilin; Carter, Emily A.

2012-07-01

Hematite (α-Fe2O3) is a promising candidate for use in photovoltaic (PV) and photoelectrochemical devices. Its poor conductivity is one major drawback. Doping hematite either p-type or n-type greatly enhances its measured conductivity and is required for potential p-n junctions in PVs. Here, we study hole transport in pure and doped hematite using an electrostatically embedded cluster model with ab initio quantum mechanics (unrestricted Hartree-Fock theory). Consistent with previous work, the model suggests that hole hopping is via oxygen anions for pure hematite. The activation energy for hole mobility is predicted to be at least 0.1 eV higher than the activation energy for electron mobility, consistent with the trend observed in experiments. We examine four dopants—magnesium(II), nickel(II), copper(II), and manganese(II/III) in direct cation substitution sites—to gain insight into the mechanism by which conductivity is improved. The activation energies are used to assess qualitative effects of different dopants. The hole carriers are predicted to be attracted to O anions near the dopants. The magnitude of the trapping effect is similar among the four dopants in their +2 oxidation states. The multivalent character of Mn doping facilitates local hole transport around Mn centers via a low-barrier O-Mn-O pathway, which suggests that higher hole mobility can be achieved with increasing Mn doping concentration, especially when a network of these low-barrier pathways is produced. Our results suggest that the experimentally observed conductivity increase in Mg-, Ni-, and Cu-doped p-type hematite is mostly due to an increase in hole carriers rather than improved mobility, and that Mg-, Ni-, and Cu-doping perform similarly, while the conductivity of Mn-doped hematite might be significantly improved in the high doping concentration limit.

Influence of oxygen vacancies on the magnetic and electrical properties of La1-xSrxMnO3-x/2 manganites

NASA Astrophysics Data System (ADS)

Trukhanov, S. V.; Lobanovski, L. S.; Bushinsky, M. V.; Khomchenko, V. A.; Pushkarev, N. V.; Troyanchuk, I. O.; Maignan, A.; Flahaut, D.; Szymczak, H.; Szymczak, R.

2004-11-01

The crystal structure, magnetization and electrical transport depending on the temperature and magnetic field for the doped stoichiometric La_{1-x}^{3 + } Sr_x^{2 + } Mn_{1-x}^{3 + } Mn_x^{4 + } O_3^{2-} as well as anion-deficient La_{1-x}^{3 + } Sr_x^{2 + } Mn^{3 + }O_{3-x/2}^{2-} (0le x le 0.30) ortomanganite systems have been experimentally studied. It is established that the stochiometric samples in the region of the 0 le x le 0.125 are an O'-orthorhombic perovskites whereas in the 0.175 le x le 0.30 - a rhombohedric. For the anion-deficient system the symmetry type of the unit cell is similar to the stoichiometric one. As a doping level increases the samples in the ground state undergo a number of the magnetic transitions. It is assumed that the samples with the large amount of oxygen vacancies are a cluster spin glasses (0.175 < x le 0.30) and temperature of the magnetic moment freezing is 40 K. All the anion-deficient samples are semiconductors and show considerable magnetoresistance over a wide temperature range with a peak for the x = 0.175 only. Concentration dependences of the spontaneous magnetization and magnetic ordering temperature for the anion-deficient La_{1-x}^{3 + } Sr_x^{2 + } Mn^{3 + }O_{3-x/2}^{2-} system have been established by the magnetic measurements and compared with those for the stoichiometric La_{1-x}^{3 + } Sr_x^{2 + } Mn_{1-x}^{3 + } Mn_x^{4 + } O_3^{2-} one. The magnetic propeprties of the anion-deficient samples may be interpreted on the base of the superexchange interaction and phase separation (chemical disorder) models.

Light-induced absorption and its relaxation under illumination of continuous wave ultraviolet light in Mn-doped near-stoichiometric LiNbO{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Youwen; Kitamura, Kenji; Takekawa, Shunji

2005-04-01

The steady-state light-induced absorption and the temporal relaxation behavior under illumination of cw ultraviolet light in Mn-doped near-stoichiometric LiNbO{sub 3} with different crystal compositions are investigated. The ultraviolet-light-induced absorption has been assigned to small polarons Nb{sub Li}{sup 4+} by measuring the absorption spectra at room temperature. The dependences of relaxation behaviors (time constant and stretching factor) of light-induced absorption on various illumination conditions (intensity, polarization) and temperature are presented, which are very different from those observed in Fe-doped LiNbO{sub 3} illuminated with highly intense light pulse, though the temporal relaxation follows the same stretched-exponential decay behavior in both cases. Themore » results are explained reasonably by using the model of distance-dependent electron transition probabilities between localized deep traps and small polarons without any additional assumptions, and discussed to tailor doped near-stoichiometric LiNbO{sub 3} crystals for two-color holographic recording with cw laser light.« less

EMR studies of the internal motion of Mn4+ ions in the Sr overdoped (La1-xSrx)(Ga1-yMny)O3 (x/y up to 8) supplemented by magnetic and optical spectroscopy measurements

NASA Astrophysics Data System (ADS)

Aleshkevych, Pavlo; Fink-Finowicki, Jan; Zayarnyuk, Tatiana; Radelytskyi, Igor; Berkowski, Marek; Rudowicz, Czeslaw; Gnutek, Pawel

2015-06-01

The effect of the Sr doping on electronic structure in single crystals of (La1-xSrx)(Ga1-yMny)O3 solid solutions (LSGM) is investigated by means of electron magnetic resonance (EMR). The EMR results are supplemented by magnetic susceptibility and optical spectroscopy measurements. The compositions with small concentration of Mn doping (y < 1%) and overdoped content of Sr (the ratio x(Sr)/y(Mn) up to 8) are used to maximally enhance the role of divalent doping. The experimental results provide evidence of the holes delocalization in the overdoped compound (x(Sr)/y(Mn) > 1). This delocalization is accompanied by appearance of the new charge transfer transitions in the optical spectrum and dynamical valence change of manganese atoms. Additionally we observe the thermally activated narrowing of resonance EMR lines due to the internal motion, which is characterized by the energy barrier depending strongly on the ratio x(Sr)/y(Mn). The energy barrier is found to be associated with the charge carrier (hole) self-trapped energy. Fitting the EMR spectra in three orthogonal planes to an orthorhombic spin Hamiltonian enables extracting the zero-field splitting (ZFS) parameters and the Zeeman g-factors for Mn4+ (S = 3/2) ions in LSGM. The experimental ZFS parameters are modeled using superposition model analysis based on an orthorhombic symmetry approximation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ying; Yang, Feng; Lee, Sungsik

Facile fabrication of manganese oxide (MnO x, 0 < x < 2) and nitrogen (N) co-doped carbon microspheres (MnO x-N-CS) has been firstly developed by one-pot construction of Mn-functionalized melamine-formaldehyde (Mn-MF) resin spheres before pyrolysis. The resulting hybrids bear evenly dispersed MnO x and N moieties in situ anchored on hierarchically porous carbon microspheres formed simultaneously. The capacitive performance is greatly tailored by varying the Mn/melamine molar ratio in the synthetic mixture and pyrolysis temperature. It is found that the MnO x-N-CS hybrid (0.008 wt% Mn, pyrolyzed at 800 °C) exhibits the highest specific capacitance up to 258 F gmore » –1 at a scan rate of 1 mV s –1 (in 6 M KOH), and keeps a high capacitance retention ratio of 98% after 5000 cycles. The synergism between MnO x, N moieties and carbon spheres proves to be responsible for the remarkably improved performance, as compared to the pure carbon sphere and MnO x (N)-doped carbon sphere. Lastly, the well-developed MnO x-N-CS hybrids highlight the great potentials for widespread supercapacitor applications.« less

Insertion of lattice strains into ordered LiNi0.5Mn1.5O4 spinel by mechanical stress: A comparison of perfect versus imperfect structures as a cathode for Li-ion batteries

NASA Astrophysics Data System (ADS)

Kozawa, Takahiro; Murakami, Takeshi; Naito, Makio

2016-07-01

The Ni-doped lithium manganese oxide, LiNi0.5Mn1.5O4, has received much attention as a cathode active material in high-energy lithium-ion batteries (LIBs). This active material has two different spinel structures depending on the ordering state of the Ni and Mn ions. The ordered LiNi0.5Mn1.5O4 spinel has an inferior cathode performance than the disordered phase because of its poor electronic conductivity. However, the ordered LiNi0.5Mn1.5O4 spinel possesses the potential advantage of avoiding dissolution of the Mn ion, which is an issue for the disordered spinel. The improvement of cathode performance is important for future applications. Here, we report a unique approach to improve the cathode performance of the ordered LiNi0.5Mn1.5O4 spinel. The mechanical treatment using an attrition-type mill successfully inserted lattice strains into the ordered LiNi0.5Mn1.5O4 spinel structure without a phase transformation to the disordered phase. The insertion of lattice strains by mechanical stresses provided an increased discharge capacity and a decreased charge transfer resistance. This limited crystal structure modification improved the cathode performance. The present work has the potential for application of the mechanically treated ordered LiNi0.5Mn1.5O4 spinel as a cathode for high-energy LIBs.

Structural, magnetic and electronic structural properties of Mn doped CeO2 nanoparticles

NASA Astrophysics Data System (ADS)

Kumari, Kavita; Vij, Ankush; Hashim, Mohd.; Chae, K. H.; Kumar, Shalendra

2018-05-01

Nanoparticles of Ce1-xMnxO2, (x=0.0, 0.01, and 0.05) have been synthesized by using co-precipitation method, and then characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), near edge x-ray absorption fine structure (NEXAFS) spectroscopy and dc magnetization measurements. XRD results clearly showed that the all the samples have single phase nature and exclude the presence of any secondary phase. The average particle size calculated using XRD TEM measurements found to decrease with increase in Mn doping in the range of 4.0 - 9.0 nm. The structural parameters such as strain, interplaner distance and lattice parameter is observed to decrease with increase in doping. The morphology of Ce1-xMnxO2 nanoparticles measured using TEM micrographs indicate that nanoparticle have spherical shape morphology. Magnetic hysteresis curve for Ce1-xMnxO2, (x = 0.0, 0.01, and 0.05) confirms the ferromagnetic ordering room temperature. The value of saturation magnetization is observed to decrease with increase in temperature from 10 K to 300 K. The NEXAFS spectra measured at Ce M4,5 edge reveals that Ce-ions are in +4 valance state.

Influence of Fe substitution on structure and Raman spectra of La0.67Sr0.33MnO3: Experimental and density functional studies

NASA Astrophysics Data System (ADS)

Astik, Nidhi M.; Soni, Himadri; Jha, Prafulla K.; Sathe, Vasant

2018-07-01

We present experimental and theoretical studies on the effect of Fe doping at Mn site, on the structural, morphological, electronic and vibrational properties of La0.67Sr0.3MnO3 nanoparticle. The samples of La0.67Sr0.3MnO3 and La0.67Sr0.33Mn1-xFexO3 (x = 0.15, 0.25 and 0.35) have been prepared by ball milling route. The phase purity of these samples has been confirmed using X-ray diffraction, while compositional analysis is done using EDAX. The morphological analysis done using scanning microscope indicates the agglomeration. The vibrational analysis which is done using Raman scattering and density functional theory (DFT) calculations show a substantial shift in A1g and Eg modes with Fe doping. The Eg modes become broader with Fe doping. The UV-visible spectra were measured in the energy range of 1-5 eV and compared with DFT results. The spin polarized density functional calculations show an increase in density of states at Fermi level due to MnO6octahedra modification and significant magnetism on Fe doping. The total magnetic moment is found from 16 to 17 μB for considered concentration. The effective mass of carriers is also calculated and found increasing with increasing concentration.

Non-adiabatic molecular dynamics investigation of photoionization state formation and lifetime in Mn²⁺-doped ZnO quantum dots.

PubMed

Fischer, Sean A; Lingerfelt, David B; May, Joseph W; Li, Xiaosong

2014-09-07

The unique electronic structure of Mn(2+)-doped ZnO quantum dots gives rise to photoionization states that can be used to manipulate the magnetic state of the material and to generate zero-reabsorption luminescence. Fast formation and long non-radiative decay of this photoionization state is a necessary requirement for these important applications. In this work, surface hopping based non-adiabatic molecular dynamics are used to demonstrate the fast formation of a metal-to-ligand charge transfer state in a Mn(2+)-doped ZnO quantum dot. The formation occurs on an ultrafast timescale and is aided by the large density of states and significant mixing of the dopant Mn(2+) 3dt2 levels with the valence-band levels of the ZnO lattice. The non-radiative lifetime of the photoionization states is also investigated.

Energy Migration Upconversion in Manganese(II)-Doped Nanoparticles.

PubMed

Li, Xiyan; Liu, Xiaowang; Chevrier, Daniel M; Qin, Xian; Xie, Xiaoji; Song, Shuyan; Zhang, Hongjie; Zhang, Peng; Liu, Xiaogang

2015-11-02

We report the synthesis and characterization of cubic NaGdF4:Yb/Tm@NaGdF4:Mn core-shell structures. By taking advantage of energy transfer through Yb→Tm→Gd→Mn in these core-shell nanoparticles, we have realized upconversion emission of Mn(2+) at room temperature in lanthanide tetrafluoride based host lattices. The upconverted Mn(2+) emission, enabled by trapping the excitation energy through a Gd(3+) lattice, was validated by the observation of a decreased lifetime from 941 to 532 μs in the emission of Gd(3+) at 310 nm ((6)P(7/2)→(8)S(7/2)). This multiphoton upconversion process can be further enhanced under pulsed laser excitation at high power densities. Both experimental and theoretical studies provide evidence for Mn(2+) doping in the lanthanide-based host lattice arising from the formation of F(-) vacancies around Mn(2+) ions to maintain charge neutrality in the shell layer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superexchange Effects on Oxygen Reduction Activity of Edge-Sharing [Cox Mn1-x O6 ] Octahedra in Spinel Oxide.

PubMed

Zhou, Ye; Sun, Shengnan; Xi, Shibo; Duan, Yan; Sritharan, Thirumany; Du, Yonghua; Xu, Zhichuan J

2018-03-01

Mn-Co containing spinel oxides are promising, low-cost electrocatalysts for the oxygen reduction reaction (ORR). Most studies are devoted to the design of porous Mn-Co spinels or to strongly coupled hybrids (e.g., MnCo 2 O 4 /N-doped-rmGO) to maximize the mass efficiency. The lack of analyses by metal oxide intrinsic activity (activity normalized to catalysts' surface area) hinders the development of fundamental understanding of the physicochemical principles behind the catalytic activities. A systematic study on the composition dependence of ORR in ZnCo x Mn 2- x O 4 (x = 0.0-2.0) spinel is presented here with special attention to the role of edge sharing [Co x Mn 1- x O 6 ] octahedra in the spinel structure. The ORR specific activity of ZnCo x Mn 2- x O 4 spans across a potential window of 200 mV, indicating an activity difference of ≈3 orders of magnitude. The curve of composition-dependent ORR specific activity as a function of Co substitution exhibits a volcano shape with an optimum Mn/Co ratio of 0.43. It is revealed that the modulated e g occupancy of active Mn cations (0.3-0.9), as a consequence of the superexchange effect between edge sharing [CoO 6 ] and [MnO 6 ], reflects the ORR activity of edge sharing [Co x Mn 1- x O 6 ] octahedra in the ZnCo x Mn 2- x O 4 spinel oxide. These findings offer crucial insights in designing spinel oxide catalysts with fine-tuned e g occupancy for efficient catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced ferromagnetic order in Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} featuring canted [MnO{sub 4}]{sub ∞} spin chains of mixed-valent Mn(III)/Mn(IV). Aliovalent substitution of the Sr{sub 4−x}Ln{sub x}Mn{sup III}{sub 2+x}Mn{sup IV}{sub 1−x}O{sub 3}(GeO{sub 4}){sub 3} solid-solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

West, J. Palmer; Sulejmanovic, Dino; Becht, Gregory

2013-10-15

Crystals of Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0; x∼0.15 for Ln=La, Pr, Nd, Sm. Eu, Gd, Dy; x∼0.3 for Ln=Gd) were isolated upon using high-temperature, solid-state methods in molten-salt media. These compounds are isostructural with the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} (Ln=La, Sm, Gd) series that contains the same [MnO{sub 4}]{sub ∞} spin chains. The synthesis of the Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0) phase was carried out by a double aliovalent substitution with respect to the Sr{sup 2+} and Ge{sup 4+} ions that replace Na{sup +}/Ln{sup 3+} and As{sup 5+} in Na{sub 3}LnMn{submore » 3}O{sub 3}(AsO{sub 4}){sub 3}, respectively. The title series contains mixed-valent Mn(III)/Mn(IV) and shows a limited range of solid solution, both of which were not observed in the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series. To form the Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} solid solution, one of the Sr{sup 2+} sites, i.e., the original Ln-site in Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}, is partially substituted by Ln{sup 3+} in a statistical disorder of Sr{sub 1−x}/Ln{sub x}. Initial magnetic investigations of selected derivatives reveal higher ferromagnetic ordering temperatures than those reported for the Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series, presumably attributed to a lesser degree of canting as a result of introducing non-Jahn–Teller Mn{sup 4+} ions. Also intriguing is the observation of multiple anomalies at low temperatures which appear to be of electronic origins. - Graphical abstract: Sr{sub 4−x}Ln{sub x}Mn(III){sub 2+x}Mn(IV){sub 1−x}O{sub 3}(GeO{sub 4}){sub 3}. Display Omitted - Highlights: • Double aliovalent substitution: Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} with respect to Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}. • Solid solution with respect to statistical disorder of Sr{sub 1−x}Ln{sub x} in one of the two Sr sites. • Mn{sup 3+}/Mn{sup 4+} magnetic ions are spatially arranged in a triangular kagomé fashion. • Enhanced ferromagnetic ordering attributed to doping non-Jahn–Teller Mn{sup 4+}.« less

Effect of Synthesis Temperature on Structure and Magnetic Properties of (La,Nd)0.7Sr0.3MnO3 Nanoparticles.

PubMed

Shlapa, Yulia; Solopan, Sergii; Bodnaruk, Andrii; Kulyk, Mykola; Kalita, Viktor; Tykhonenko-Polishchuk, Yulia; Tovstolytkin, Alexandr; Belous, Anatolii

2017-12-01

Two sets of Nd-doped La 0.7 Sr 0.3 MnO 3 nanoparticles were synthesized via sol-gel method with further heat treatment at 1073 and 1573 K, respectively. Crystallographic and magnetic properties of obtained nanoparticles were studied, and the effect of synthesis conditions on these properties was investigated. According to X-ray data, all particles crystallized in the distorted perovskite structure. Magnetic parameters, such as saturation magnetization, coercivity, Curie temperature, and specific loss power, which is released on the exposure of an ensemble of nanoparticles to AC magnetic field, were determined for both sets of samples. The correlation between the values of Curie temperature and maximal heating temperature under AC magnetic field was found. It was revealed that for the samples synthesized at 1573 K, the dependences of crystallographic and magnetic parameters on Nd content were monotonous, while for the samples synthesized at 1073 K, they were non-monotonous. It was concluded that Nd-doped La 0.7 Sr 0.3 MnO 3 nanoparticles are promising materials for self-controlled magnetic hyperthermia applications, but the researchers should be aware of the unusual behavior of the particles synthesized at relatively low temperatures.

Magnetic properties of rare-earth-doped La0.7Sr0.3MnO3.

PubMed

Veverka, Pavel; Kaman, Ondřej; Knížek, Karel; Novák, Pavel; Maryško, Miroslav; Jirák, Zdeněk

2017-01-25

Rare-earth-doped ferromagnetic manganites La 0.63 RE 0.07 Sr 0.30 MnO 3 (RE  =  Gd, Tb, Dy, and Ho) are synthesized in the form of sintered ceramics and nanocrystalline phases with the mean size of crystallites  ≈30 nm. The electronic states of the dopants are investigated by SQUID magnetometry and theoretically interpreted based on the calculations of the crystal field splitting of rare-earth energy levels. The samples show the orthorhombic perovskite structure of Ibmm symmetry, with a complete FM order of Mn spins in bulk and reduced order in nanoparticles. Non-zero moments are also detected at the perovskite A sites, which can be attributed to magnetic polarization of the rare-earth dopants. The measurements in external field up to 70 kOe show a standard Curie-type contribution of the spin-only moments of Gd 3+ ions, whereas Kramers ions Dy 3+ and non-Kramers ions Ho 3+ contribute by Ising moments due to their doublet ground states. The behaviour of non-Kramers ions Tb 3+ is anomalous, pointing to singlet ground state with giant Van Vleck paramagnetism. The Tb 3+ doping leads also to a notably increased coercivity compared to other La 0.63 RE 0.07 Sr 0.30 MnO 3 systems.

Bismuth Oxide Nanoparticles Partially Substituted with EuIII, MnIV, and SiIV: Structural, Spectroscopic, and Optical Findings.

PubMed

Ortiz-Quiñonez, José-Luis; Zumeta-Dubé, Inti; Díaz, David; Nava-Etzana, Noel; Cruz-Zaragoza, Epifanio; Santiago-Jacinto, Patricia

2017-03-20

Interest in nanostructured partially substituted bismuth oxides has been increasing over the last years. Research on new synthesis methods, properties, and possible uses for these oxides is needed. The objective of this paper is to synthesize β-Bi 2 O 3 , β-Bi 2 O 3 :Eu 3+ , β-Bi 2 O 3 :Mn 4+ , Bi 12 Bi 0.8 O 19.2 , Bi 12 Bi 0.8 O 19.2 /Li + , Bi 12 MnO 20 , and Bi 12 SiO 20 nanoparticles and to investigate their structural, spectroscopic, and optical changes. Some of the causes that generated their properties are also discussed. These materials are important because the doping or partial substitution of bismuth oxide with these cations (Eu 3+ , Mn 4+ , and Si 4+ ) modifies some properties such as optical absorption, reactivity toward CO 2 , among others. X-ray diffraction (in powders), high-resolution transmission electron microscopy, Fourier transform infrared (FTIR), resonance Raman scattering, diffuse reflectance, and solid-state magic-angle-spinning 29 Si NMR were used for the characterization of the synthesized materials. We found that partial substitution of yellow Bi 12 Bi 0.8 O 19.2 with Mn 4+ and Si 4+ changed the color to green and whitish, respectively. New bands in the Raman scattering and FTIR spectra of these oxides are deeply discussed. Raman scattering spectroscopy was a valuable and reliable technique to detect the Eu 3+ and Mn 4+ cations as dopants in the bismuth oxides. The 29 Si chemical shift (δ) in Bi 12 SiO 20 was -78.16 ppm, whereas in SiO 2 , it was around -110 ppm. This considerable shift in Bi 12 SiO 20 occurred because of an increased shielding of the Si nucleus in the Si(O) 4 tetrahedron. This shielding was provided by the low-electronegativity and highly polarizable Bi cations. The isovalent doping of β-Bi 2 O 3 nanoparticles with Eu 3+ enhanced their thermal stability over 400 °C. Variation in the optical absorption and reactivity toward the acidic CO 2 molecule of the partially substituted bismuth oxides was explained on the basis of the optical basicity and ionic-covalent parameter concepts. Some possible uses for the synthesized oxides are suggested.

Spectroscopic and ultrasonic investigations on structural characterization of borate glass specimen doped with transition metal ions

NASA Astrophysics Data System (ADS)

Sathish, K.; Thirumaran, S.

2015-08-01

The present work describes the glass samples of composition (x% V2O5-(80-x)% B2O3-20% Na2CO3) VBS glass system and (x% MnO2-(80-x)% B2O3-20% Na2CO3) in MBS glass system with mol% ranging from x = 3, 6, 9, 12, 15 and 18 in steps of 3 mol% are prepared by melt quenching technique. For these prepared glass systems, sound velocity (longitudinal and shear velocities) and density have been measured. The sound velocity (longitudinal and shear) was measured by using pulse-echo technique at 5 MHz. The XRD study was carried to out to ascertain the amorphous nature of the glass specimen. Using these measured values, the elastic moduli, Poisson's ratio, Debye temperature, acoustic impedance and thermal expansion coefficient of the two glass systems were evaluated. The elastic and mechanical properties of the prepared glass systems are analyzed from ultrasonic study and the structural characterization from spectroscopic study. The effects due to the doping of transition metal ions with borate have been discussed. In the V2O5 doped glass system, (VBS glass system) the sound velocity, density and elastic moduli, steeply increases after 12 mol% comparatively with MnO2 doped glass system (VBS glass system). The present study critically observes the doping of V2O5 with borate enhances the strengthening of network linkage and hardening of the glassy network structure than MnO2. The IR spectral analysis reveals depolymerization of the borate network and conversion of BO3 or BO4 units with the formation of non-bridging oxygen. The FTIR spectral studies confirm the presence of various functional groups of the sample. FTIR spectrum of sample exhibits broad absorption bands indicating the wide distribution of borate structural units. The effect of Na2CO3, V2O5 and MnO2 contents on the structures of borate glass is evaluated from the FTIR spectra. The topological aspects of the prepared glass samples are exhaustively reported from SEM micrographs.

Structural and critical current properties in Al-doped MgB 2

NASA Astrophysics Data System (ADS)

Zheng, D. N.; Xiang, J. Y.; Lang, P. L.; Li, J. Q.; Che, G. C.; Zhao, Z. W.; Wen, H. H.; Tian, H. Y.; Ni, Y. M.; Zhao, Z. X.

2004-08-01

A series of Al-doped Mg 1- xAl xB 2 samples have been fabricated and systematic study on structure and superconducting properties have been carried out for the samples. In addition to a structural transition observed by XRD, TEM micrographs showed the existence of a superstructure of double c-axis lattice constant along the direction perpendicular to the boron honeycomb sheet. In order to investigate the effect of Al doping on flux pinning and critical current properties in MgB 2, measurements on the superconducting transition temperature Tc, irreversible field Birr and critical current density Jc were performed too, for the samples with the doping levels lower than 0.15 in particular. These experimental observations were discussed in terms of Al doping induced changes in carrier concentration.

Effects of Nickel Doping on the Multiferroic and Magnetic Phases of MnWO 4

DOE PAGES

Poudel, N.; Lorenz, B.; Lv, B.; ...

2015-12-15

There are various orders in multiferroic materials with a frustrated spiral spin modulation inducing a ferroelectric state are extremely sensitive to small perturbations such as magnetic and electric fields, external pressure, or chemical substitutions. A classical multiferroic, the mineral Hubnerite with chemical formula MnWO 4, shows three different magnetic phases at low temperature. The intermediate phase between 7.5K < T < 12.7K is multiferroic and ferroelectricity is induced by an inversion symmetry breaking spiral Mn-spin order and strong spin-lattice interactions. Furthermore, the substitution of Ni 2+ (spin 1) for Mn 2+ (spin 5/2) in MnWO 4 and its effects onmore » the magnetic and multiferroic phases are studied. The ferroelectric phase is stabilized for low Ni content (up to 10%). Upon further Ni doping, the polarization in the ferroelectric phase is quickly suppressed while a collinear and commensurate magnetic phase, characteristic of the magnetic structure in NiWO 4, appears first at higher temperature, gradually extends to lower temperature, and becomes the ground state above 30% doping. Between 10% and 30%, the multiferroic phase coexists with the collinear commensurate phase. In this concentration region, the spin spiral plane is close to the a-b plane which explains the drop of the ferroelectric polarization. Finally, the phase diagram of Mn 1-xNi xWO 4 is derived by a combination of magnetic susceptibility, specific heat, electric polarization, and neutron scattering measurements.« less

Influence of Ga vacancies, Mn and O impurities on the ferromagnetic properties of GaN micro- and nanostructures

NASA Astrophysics Data System (ADS)

Guzmán, G.; Escudero, R.; Silva, R.; Herrera, M.

2018-04-01

We present a study of the influence of gallium vacancy (VGa) point defects on the ferromagnetic properties of GaN:Mn and GaN:Mn,O micro- and nanostructures. Results demonstrate that the generation of these point defects enhances the ferromagnetic signal of GaN:Mn microstructures, while incorporation of oxygen as an impurity inhibits this property. XPS measurements revealed that Mn impurities in ferromagnetic GaN:Mn samples mainly exhibit a valence state of 2+. Cathodoluminescence (CL) spectra from Mn-doped GaN samples displayed emissions centered at about 1.97 eV, attributed to transitions between the 4T1-6A1 states of the Mn2+ d orbitals, and emissions centered at 2.45 and 2.9 eV, associated with the presence of VGa. CL measurements also revealed a blue shift of the GaN band-edge emission generated by the expansion of the wurtzite lattice due to Mn incorporation, which was confirmed by XRD measurements. These latter measurements also revealed an amorphization of GaN:Mn due to the incorporation of oxygen as impurities. The GaN:Mn samples were synthesized by thermal evaporation of GaN and MnCO3 powders onto Ni0.8Cr0.2/Si(100) in a horizontal furnace operated at low vacuum. The residual air inside the system was used as a source of oxygen during the synthesis of Mn and O co-doped GaN nanostructures. Mn and O impurities were incorporated into the nanostructures at different concentrations by varying the growth temperature. Energy Dispersive Spectroscopy, XRD, and XPS measurements confirmed that the obtained samples predominantly consisted of GaN.

Synthesis and structural studies on cerium substituted La0.4Ca0.6MnO3 as solid oxide fuel cell electrode material

NASA Astrophysics Data System (ADS)

Singh, Monika; Kumar, Dinesh; Singh, Akhilesh Kumar

2018-04-01

For solid oxide fuel cell electrode material, calcium doped lanthanum manganite La0.4Ca0.6MnO3 (LCMO) and cerium-incorporated on Ca-site with composition La0.40Ca0.55Ce0.05MnO3 (LCCMO) were synthesized using most feasible and efficient glycine-nitrate method. The formation of crystalline single phase was confirmed by x-ray diffraction (XRD). The Rietveld analysis reveals that both systems crystallize into orthorhombic crystal structure with Pnma space group. Additionally, 8 mole % Y2O3 stabilized ZrO2 (8YSZ) solid electrolyte was also synthesized using high energy ball mill to check the reaction with electrode materials. It was found that the substitution of Ce+4 cations in LCMO perovskite suppressed formation of undesired insulating CaZrO3 phase.

Layered Li-Mn-M-oxides as cathodes for Li-ion batteries:. Recent trends

NASA Astrophysics Data System (ADS)

Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R.

2002-12-01

There is an increasing demand for manganese (Mn) based mixed oxides which can effectively replace the presently used LiCoO2 as cathode in Li-ion batteries (LIB). The well-studied spinel, LiMn2O4 and its doped derivatives give a capacity of 100-120 mAh/g, but show capacity-fading on cycling especially above 55°C. The layered LiMnO2, isostructural to LiCoO2 (so called O3-structure) can be a viable cathode. However, studies have shown that it undergoes conversion to spinel structure on cycling and thus gives capacity-fading. Other alternative systems recently studied are: O2-structured layered Li-M-Mn-oxides with the general formula Li(2/3)+x(MyMn1-y)O2, M = Li, Ni, Co; x ≤ 0.33 and y = 0.1-0.67, O3-Li(Ni1/2Mn1/2)O2, Li(NixCo1-2xMnx)O2, and M'-substituted Li2MnO3 (M' = Ni, Co, Cr). Some of them are shown to have stable cycling performance, good rate-capability and structural stability over charge-discharge cycling in the 2.5-4.6 V region. Further, the electrochemical processes in the above mixed oxides have been shown to involve Ni2+/4+ or Cr3+/6+ redox couple, thus invoking novel ideas to develop new cathode materials. A brief review of the work done on the above O2- and O3-layered Li-Mn-M-oxides (M = metal) as cathodes for LIB is presented.

CNT supported Mn-doped ZnO nanoparticles: simple synthesis and improved photocatalytic activity for degradation of malachite green dye under visible light

NASA Astrophysics Data System (ADS)

Mohamed, R. M.; Shawky, Ahmed

2018-03-01

Hexagonal ZnO nanoparticles doped with Mn and supported with a minor amount of carbon nanotubes (CNTs) were synthesized through a simple coprecipitation-ultrasonication process with high yield. The effect of Mn doping, as well as CNTs addition on structure, surface morphology and texture, optical and electronic properties, was studied. We found that just 1% Mn doping and 1% CNT addition on ZnO showed the best crystallinity, highest surface area, improved visible light absorption, and a lowest estimated band gap of 2.6 eV with minimum charge recombination as revealed from photoluminescence spectra. The application of the optimum composition of the synthesized sample for the photodegradation of malachite green dye showed enhanced photocatalytic activity > 95% under visible light irradiation within 120 min at a minimum dosage of 0.1 g L-1 without any using of hole scavenger or changing the pH. This work highlighting the humble preparation procedure and develops photocatalysis research for real industrial applications.

Investigating the effect of Cd-Mn co-doped nano-sized BiFeO3 on its physical properties

NASA Astrophysics Data System (ADS)

Ishaq, B.; Murtaza, G.; Sharif, S.; Azhar Khan, M.; Akhtar, Naeem; Will, I. G.; Saleem, Murtaza; Ramay, Shahid M.

This work deals with the investigation of different effects on the structural, magnetic, electronic and dielectric properties of Cd and Mn doped Bi0.75Cd0.25Fe1-xMnxO3 multiferroic samples by taking fixed ratios of Cd and varying the Mn ratio with values of x = 0.0, 0.5, 0.10 and 0.15. Cd-Mn doped samples were synthesized chemically using a microemulsion method. All the samples were finally sintered at 700 °C for 2 h to obtain the single phase perovskites structure of BiFeO3 materials. The synthesized samples were characterized by different techniques, such as X-ray diffractometry (XRD), Scanning Electron Microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), LCR meter and magnetic properties using VSM. XRD results confirm BFO is a perovskite structure having crystallite size in the range of 24-54 nm. XRD results also reveal observed structural distortion due to doping of Cd at the A-site and Mn at the B-site of BFO. SEM results depict that, as the substitution of Cd-Mn increases in BFO, grain size decreases up to 30 nm. FTIR spectra showed prominent absorption bands at 555 cm-1 and 445 cm-1 corresponding to the stretching vibrations of the metal ions complexes at site A and site B, respectively. Variation of dielectric constant (ɛ‧) and loss tangent (tan δ) at room temperature in the range of 1 MHz to 3 GHz have been investigated. Results reveal that with Cd-Mn co doping a slight decrease in dielectric constant have been observed. Magnetic properties of Cd-Mn doped pure BFO samples have been studied at 300 K. Results reveal that undoped BiFeO3 exhibits weak ferromagnetic ordering due to the canting of its spin. Increase in magnetization and decrease in coercivity is a clear indication that a material can be used in high density recording media and memory devices.

Revival of ferromagnetic behavior in charge-ordered Pr0.75Na0.25MnO3 manganite by ruthenium doping at Mn site and its MR effect

NASA Astrophysics Data System (ADS)

Elyana, E.; Mohamed, Z.; Kamil, S. A.; Supardan, S. N.; Chen, S. K.; Yahya, A. K.

2018-02-01

Ru doping in charge-ordered Pr0.75Na0.25Mn1-xRuxO3 (x = 0-0.1) manganites was studied to investigate its effect on structure, electrical transport, magnetic properties, and magnetotransport properties. DC electrical resistivity (ρ), magnetic susceptibility, and χ' measurements showed that sample x = 0 exhibits insulating behavior within the entire temperature range and antiferromagnetic (AFM) behavior below the charge-ordering (CO) transition temperature TCO of 221 K. Ru4+ substitution (x>0.01) suppressed the CO state, which resulted in the revival of paramagnetic to ferromagnetic (FM) transition at the Curie temperature Tc, increasing from 120 K (x = 0.01) to 193 K (x = 0.1). Deviation from the Curie-Weiss law above Tc in the 1/χ' versus T plot for x = 0.01 doped samples indicated the existence of Griffiths phase with Griffith temperature at 169 K. Electrical resistivity measurements showed that Ru4+ substitution increased the metallic-to-insulating transition temperature TMI from 144 K (x = 0.01) to 192 K (x = 0.05) due to enhanced double-exchange mechanism, but TMI decreased to 176 K (x = 0.1) probably due to the existence of AFM clusters within the FM domain. The present work also discussed the possible theoretical models at the resistivity curve of Pr0.75Na0.25Mn1-xRuxO3 (x = 0-0.1) for the entire temperature range.

Synthesis and characterization of cathode materials for lithium ion-rechargeable batteries

NASA Astrophysics Data System (ADS)

Nieto Ramos, Santander

Lithium intercalation materials are of special interest for cathodes in rechargeable lihium-ion batteries, because they are capable of reversibly intercalating lithium ions without altering the main unit. We developed a novel solution-based route for the synthesis of these lithium intercalates oxides. The first part of this work was devoted to the optimization of chemical solution process parameters in order to correlate their electrochemical properties. It was found that the lattice parameters and the crystallite size increase, whereas the lattice strain decreases with the increase in calcinations temperature. Powders annealed at 700°C for 15 h yielded best electrochemical performance. The electrochemical performance of substituted Li1.2Mn2O 4, Li1.2Mn1.8O4, Li1.2Cr 0.05Mn1.95O4, and Li1.2Cr0.05 Mn1.75O4 spinel electrodes in lithium cell has been studied. The electrochemical data showed that the Li and Cr dopant effect improves the cycleablility of spinel LiMn2O4 electrodes. The second part of this dissertation was devoted to improve the rate capabilities of these cathode materials by growing nano-size cathode particles and also by cation co-doping. Though the discharge capacity of these nano-crystalline cathodes was equivalent to their microcrystalline counterpart, these exhibited capacity fading in the 4V range. Through a combined X-ray diffraction, micro-Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) analyses, we correlated the observed capacity fading with the onset of Jahn-Teller (J-T) distortion toward the end of the discharge in the cut-off limit between 4.2 and 3.2V. It was postulated that J-T distortion is the dominant fading mechanism of these nano-crystalline cathodes then by increasing the average oxidation state of the Mn ion in a virgin lithium manganate cathode, the onset of such distortion towards the end of the discharge could be delayed, and therefore, the cycleability of these cathodes could be improved. By synthesizing lithium and aluminum ion co-doped lithium manganate particles, we could increase the average oxidation state of Mn ions in the virgin electrodes. Indeed, the cycleability of these co-doped cathodes was dramatically improved which supports our population. The third part of this thesis was devoted to synthesis and electrochemical properties of layered compounds. Lithium nickel oxides derivatives are promising positive materials for the next generation of lithium-ion batteries. Partial substitution of certain cations for nickel in this family of oxides which satisfies the demanding requirements for rechargeable battery applications. In this part the interest is focused on the effect of simultaneous cobalt as well as aluminum doping was studied to understand their effect on the phase formation behavior and electrochemical properties of solution derived lithium nickel oxide cathode materials for rechargeable batteries. (Abstract shortened by UMI.)

Effects of Dopant on the Dielectric Properties of CaZrO3 Ceramic Sintered in a Reducing Atmosphere

NASA Astrophysics Data System (ADS)

Lee, W. S.; Su, C. Y.; Lee, Y. C.; Lin, S. P.; Yang, Tony

2006-07-01

In this study, the influence of CaZrO3 doped with three dopants, SiO2, MnO, and Nb2O5, and then sintered in a reducing atmosphere on microstructure, phase formation, and electrical properties is investigated. SiO2 plays the role of sintering aid to enhance the density of CaZrO3 leading to better performance of electrical properties as a function of SiO2 content. MnO, and Nb2O5 were incorporated into the Zr-site of CaZrO3 to make stoichometric CaZrO3 into non-stoichiometric CaZrO3 with Zr excess resulting in the formation of a second phase, CaZr4O9, which has a lower dielectric constant (13) in comparison with that of the main phase of CaZrO3 (32). Thus, the dielectric constant of CaZrO3 doped with Nb2O5, or MnO is decreased markedly. In addition, Mn+2 incorporated into Zr-sites of CaZrO3 plays the role of acceptor, which compensates for the number of conduction electrons and contributes to better performance of electrical properties such as insulation resistance and \\tanδ. Conversely, Nb+5 incorporated into Zr-sites of CaZrO3 plays the role of donor and provides more conduction electrons, leading to poor performance of electrical properties.

MgB2 wire diameter reduction by hot isostatic pressing—a route for enhanced critical current density

NASA Astrophysics Data System (ADS)

Morawski, A.; Cetner, T.; Gajda, D.; Zaleski, A. J.; Häßler, W.; Nenkov, K.; Rindfleisch, M. A.; Tomsic, M.; Przysłupski, P.

2018-07-01

The effect of wire diameter reduction on the critical current density of pristine MgB2 wire was studied. Wires were treated by a hot isostatic pressing method at 570 °C and at pressures of up to 1.1 GPa. It was found that the wire diameter reduction induces an increase of up to 70% in the mass density of the superconducting cores. This feature leads to increases in critical current, critical current density, and pinning force density. The magnitude and field dependence of the critical current density are related to both grain connectivity and structural defects, which act as effective pinning centers. High field transport properties were obtained without doping of the MgB2 phase. A critical current density jc of 3500 A mm‑2 was reached at 4 K, 6 T for the best sample, which was a five-fold increase compared to MgB2 samples synthesized at ambient pressure.

Fabrication and properties of multifilamentary MgB 2 wires by in-situ powder-in-tube process

NASA Astrophysics Data System (ADS)

Wang, Q. Y.; Jiao, G. F.; Liu, G. Q.; Xiong, X. M.; Yan, S. C.; Zhang, P. X.; Sulpice, A.; Mossang, E.; Feng, Y.; Yan, G.

2010-11-01

We have fabricated the long TiC-doped MgB2 wires with 6 filaments by in-situ powder-in-tube method using Nb as the barrier and copper as the stabilizer. To improve the strength of wires, the Nb-core was used as the central filament. The transport engineering critical current density (Jce) of the samples sintered at different temperature were measured, which reaches 2.5 × 104 A/cm2 at 4.2 K, 5 T. 100 m MgB2 wires with different diameter were wound into coils and the transport critical current (Ic) of the coil were measured at 30 K in self-field. The Jce value 100 m coil achieves 1.1 × 104 A/cm2 in 1.2 mm wire. The reasons leading to the enhancement of high field Jce were discussed. The results show a good potential to fabricate high performance MgB2 wires and tapes at ambient pressure on an industrial scale.

A comprehensive study on electrochemical performance of Mn-surface-modified LiNi0.8Co0.15Al0.05O2 synthesized by an in situ oxidizing-coating method

NASA Astrophysics Data System (ADS)

Huang, Bin; Li, Xinhai; Wang, Zhixing; Guo, Huajun; Shen, Li; Wang, Jiexi

2014-04-01

The degradation of Ni-rich LiNi0.8Co0.15Al0.05O2 cathode material is successfully suppressed via a facile in situ oxidizing-coating method. KMnO4 is used as not only a Mn source but also an oxidant. X-ray diffraction (XRD) and scanning electron microscope (SEM) results demonstrate that the structure and morphology of the KMnO4-pretreated sample are the same as the pristine one. X-ray photoelectron spectroscopy (XPS) confirms that the valence state of Mn is +4 and the Ni3+ ions are partly reduced to Ni2+ when the material is doped with Mn4+. Besides, the Mn4+ ions are proved to distribute uniformly on the surface of the materials particles through energy dispersive spectrometer (EDS) and EDS elemental mapping. And it is confirmed that the concentration of Ni in the outer layer is reduced by the Mn-surface-modification. From the electrochemical characterizations, it is confirmed that the presence of tetravalent Mn at the surface can suppress the capacity fading during charge-discharge cycles, even under elevated temperature and overcharge conditions, and can prevent the material from deterioration during storage in air.

Top-Down Strategy to Synthesize Mesoporous Dual Carbon Armored MnO Nanoparticles for Lithium-Ion Battery Anodes.

PubMed

Zhang, Wei; Li, Jiannian; Zhang, Jie; Sheng, Jinzhi; He, Ting; Tian, Meiyue; Zhao, Yufeng; Xie, Changjun; Mai, Liqiang; Mu, Shichun

2017-04-12

To overcome inferior rate capability and cycle stability of MnO-based materials as a lithium-ion battery anode associated with the pulverization and gradual aggregation during the conversion process, we constructed robust mesoporous N-doped carbon (N-C) protected MnO nanoparticles on reduced graphene oxide (rGO) (MnO@N-C/rGO) by a simple top-down incorporation strategy. Such dual carbon protection endows MnO@N-C/rGO with excellent structural stability and enhanced charge transfer kinetics. At 100 mA g -1 , it exhibits superior rate capability as high as 864.7 mAh g -1 , undergoing the deep charge/discharge for 70 cycles and outstanding cyclic stability (after 1300 cyclic tests at 2000 mA g -1 ; 425.0 mAh g -1 remains, accompanying merely 0.004% capacity decay per cycle). This facile method provides a novel strategy for synthesis of porous electrodes by making use of highly insulating materials.

P2-type Na2/3Mn1-xAlxO2 cathode material for sodium-ion batteries: Al-doped enhanced electrochemical properties and studies on the electrode kinetics

NASA Astrophysics Data System (ADS)

Pang, Wei-Lin; Zhang, Xiao-Hua; Guo, Jin-Zhi; Li, Jin-Yue; Yan, Xin; Hou, Bao-Hua; Guan, Hong-Yu; Wu, Xing-Long

2017-07-01

Recently, sodium-ion batteries (SIBs) have been considered as the promising alternative for lithium-ion batteries. Although layered P2-type transition metal oxides are an important class of cathode materials for SIBs, there are still some hurdles for the practical applications, including low specific capacity as well as poor cycling and rate properties. In this study, the electrochemical properties of layered Mn-based oxides have been effectively improved via Al doping, which cannot only promote the formation of layered P2-type structure in the preparation processes but also stabilize the lattice during the successive Na-intercalation/deintercalation due to suppression of the Jahn-Teller distortion of Mn3+. Among the as-prepared series of Na2/3Mn1-xAlxO2 (x = 0, 1/18, 1/9, and 2/9), Na2/3Mn8/9Al1/9O2 with x = 1/9 exhibits the optimal doping effect with the best electrochemical properties, in terms of the highest specific capacity of 162.3 mA h g-1 at 0.1 C, the highest rate capability, and the best cycling stability in comparison to the undoped Na2/3MnO2 and the other two materials with different Al-doped contents. Both cyclic voltammetry at varied scan rates and galvanostatic intermittent titration technique disclose the optimal electrode kinetics (the highest Na-diffusion coefficient) of the best Na2/3Mn8/9Al1/9O2.

Solvothermal synthesis of Zn{sub 2}GeO{sub 4}:Mn{sup 2+} nanophosphor in water/diethylene glycol system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeshita, Satoru; Honda, Joji; Isobe, Tetsuhiko, E-mail: isobe@applc.keio.ac.jp

2012-05-15

The influence of aging of the suspension containing the amorphous precusors on structural, compositional and photoluminescent properties is studied to understand the mechanism on the formation of Zn{sub 2}GeO{sub 4}:Mn{sup 2+} nanoparticles during the solvothermal reaction in the water/diethylene glycol mixed solvent. Aging at 200 Degree-Sign C for 20 min forms the crystalline Zn{sub 2}GeO{sub 4} nanorods and then they grow up to {approx} 50 nm in mean length after aging for 240 min. Their interplanar spacing of (410) increases with increasing the aging time. The photoluminescence intensity corresponding to the d-d transition of Mn{sup 2+} increases with increasing themore » aging time up to 120 min, and then decreases after aging for 240 min. The photoluminescence lifetime decreases with increasing the aging time, indicating the locally concentrated Mn{sup 2+} ions. These results reveal that Mn{sup 2+} ions gradually replace Zn{sup 2+} ions near surface through repeating dissolusion and precipitation processes during prolonged aging after the complete crystallization of Zn{sub 2}GeO{sub 4}. - Graphical abstract: TEM images of Zn{sub 2}GeO{sub 4}:Mn{sup 2+} nanoparticles aged at 200 Degree-Sign C for different aging times in the mixed solvent of water and diethylene glycol. Highlights: Black-Right-Pointing-Pointer Mechanism on formation of Zn{sub 2}GeO{sub 4}:Mn{sup 2+} nanophosphor under solvothermal condition. Black-Right-Pointing-Pointer Zn{sub 2}GeO{sub 4} nanorods crystallize via amorphous precursors. Black-Right-Pointing-Pointer Gradual substitution of Mn{sup 2+} during prolonged aging. Black-Right-Pointing-Pointer Such an inhomogeneous Mn{sup 2+} doping process results in concentration quenching.« less

The effect of cation doping on the morphology, optical and structural properties of highly oriented wurtzite ZnO-nanorod arrays grown by a hydrothermal method

NASA Astrophysics Data System (ADS)

Hassanpour, A.; Guo, P.; Shen, S.; Bianucci, P.

2017-10-01

Undoped and C-doped (C: Mg2+, Ni2+, Mn2+, Co2+, Cu2+, Cr3+) ZnO nanorods were synthesized by a hydrothermal method at temperatures as low as 60 °C. The effect of doping on the morphology of the ZnO nanorods was visualized by taking their cross section and top SEM images. The results show that the size of nanorods was increased in both height and diameter by cation doping. The crystallinity change of the ZnO nanorods due to each doping element was thoroughly investigated by an x-ray diffraction (XRD). The XRD patterns show that the wurtzite crystal structure of ZnO nanorods was maintained after cation addition. The optical Raman-active modes of undoped and cation-doped nanorods were measured with a micro-Raman setup at room temperature. The surface chemistry of samples was investigated by x-ray photoelectron spectroscopy and energy-dispersive x-ray spectroscopy. Finally, the effect of each cation dopant on band-gap shift of the ZnO nanorods was investigated by a photoluminescence setup at room temperature. Although the amount of dopants (Mg2+, Ni2+, and Co2+) was smaller than the amount of Mn2+, Cu2+, and Cr3+ in the nanorods, their effect on the band structure of the ZnO nanorods was profound. The highest band-gap shift was achieved for a Co-doped sample, and the best crystal orientation was for Mn-doped ZnO nanorods. Our results can be used as a comprehensive reference for engineering of the morphological, structural and optical properties of cation-doped ZnO nanorods by using a low-temperature synthesis as an economical mass-production approach.

A spot laser modulated resistance switching effect observed on n-type Mn-doped ZnO/SiO2/Si structure.

PubMed

Lu, Jing; Tu, Xinglong; Yin, Guilin; Wang, Hui; He, Dannong

2017-11-09

In this work, a spot laser modulated resistance switching (RS) effect is firstly observed on n-type Mn-doped ZnO/SiO 2 /Si structure by growing n-type Mn-doped ZnO film on Si wafer covered with a 1.2 nm native SiO 2 , which has a resistivity in the range of 50-80 Ω∙cm. The I-V curve obtained in dark condition evidences the structure a rectifying junction, which is further confirmed by placing external bias. Compared to the resistance state modulated by electric field only in dark (without illumination), the switching voltage driving the resistance state of the structure from one state to the other, shows clear shift under a spot laser illumination. Remarkably, the switching voltage shift shows a dual dependence on the illumination position and power of the spot laser. We ascribe this dual dependence to the electric filed produced by the redistribution of photo-generated carriers, which enhance the internal barrier of the hetero-junction. A complete theoretical analysis based on junction current and diffusion equation is presented. The dependence of the switching voltage on spot laser illumination makes the n-type Mn-doped ZnO/SiO 2 /Si structure sensitive to light, which thus allows for the integration of an extra functionality in the ZnO-based photoelectric device.

Ferromagnetic properties of Mn-doped HfS2 monolayer under strain

NASA Astrophysics Data System (ADS)

Ma, Xu; Zhao, Xu; Wu, Ninghua; Xin, Qianqian; Liu, Xiaomeng; Wang, Tianxing; Wei, Shuyi

2017-12-01

Using the first-principles calculations, we investigated electronic and magnetic properties of Mn-doped HfS2 monolayer for 4% and 8% Mn concentration. We study the strain tuning of electronic and magnetic properties of 4% Mn-doped HfS2 monolayer firstly. Our results show that the Mn-doped HfS2 monolayer is magnetic nanomaterial without strain. It keeps this character until the compressive strain comes to -8%, and the magnetism disappear with lager compressive strain. With the increasing tensile strain, the doped system transforms from semiconductor to half-metallic when the tensile strain is equivalent to or greater than 5%. The largest half-metallic gap is 1.307 eV at 5% tensile strain and the magnetic moment always keeps about 3μB, which indicates that Mn-doped HfS2 monolayer can be a candidate for superior half-metallic namomaterial. Furthermore, we find two Mn dopants couple ferromagnetically via antiferromagnetic (AFM) p-d exchange interaction at the environment of 8% concentration. It keeps the properties of magnetic semiconductor under two Mn-doped configurations with different Mn-Mn separations. Our studies predict Mn-doped HfS2 monolayer under strain to be candidates for dilute magnetic semiconductors.

Effects of Mn Substitution on the Thermoelectric Properties and Thermal Excitations of the Electron-doped Perovskite Sr1-xLaxTiO3

NASA Astrophysics Data System (ADS)

Okuda, Tetsuji; Hata, Hiroto; Eto, Takahiro; Sobaru, Shogo; Oda, Ryosuke; Kaji, Hiroki; Nishina, Kousuke; Kuwahara, Hideki; Nakamura, Mitsutaka; Kajimoto, Ryoichi

2016-09-01

We studied how Mn substitution affects the thermoelectric properties and thermal excitations of the electron-doped perovskite Sr1-xLaxTiO3 by measuring its electrical and thermal transport properties, magnetization, specific heat, and inelastic neutron scattering. Slight Mn substitution with the lattice defects enhanced the Seebeck coefficient, perhaps because of coupling between itinerant electrons and localized spins or between itinerant electrons and local lattice distortion around Mn3+ ions, while it enhanced anharmonic lattice vibrations, which effectively suppressed thermal conductivity in a state of high electrical conductivity. Consequently, slight Mn substitution increased the dimensionless thermoelectric figure of merit for Sr1-xLaxTiO3 near room temperature.

Thermoelectric properties of Ca(1-x-y)Dy(x)CeyMnO3 for power generation.

PubMed

Park, K; Lee, G W; Jung, J; Kim, S-J; Lim, Y-S; Choi, S-M; Seo, W-S

2011-08-01

The sintered Ca(1-x-y)Dy(x)CeyMnO3 bodies were a single phase with a perovskite structure without any impurity phases. The calculated crystallite sizes of the Ca(1-x-y)Dy(x)CeyMnO3 were in the range of 43.3 to 63.3 nm. The composition significantly affected their microstructural and thermoelectric characteristics. The doped Dy led to both an increase in the electrical conductivity as well as the absolute value of the Seebeck coefficient, resulting in an enhanced power factor. The highest power factor (5.1 x 10(-4) Wm(-1) K(-2)) was obtained for Ca(0.8)Dy(0.2)MnO3 at 800 degrees C. In this study, we systematically discussed the thermoelectric properties of the Ca(1-x-y)Dy(x)CeyMnO3, with respect to the substitution of Dy and/or Ce for Ca.

Studies of doped LaMnO3 samples prepared by citrate combustion process

NASA Astrophysics Data System (ADS)

Dimri, M. Chandra; Khanduri, H.; Mere, A.; Stern, R.

2018-04-01

La0.95A0.05MnO3 (where A=Na, Sr, Er, Dy and Ce) powder samples were synthesized by chemical solution route and the magnetic and structural properties are reported in this paper. The pervoskite structure was confirmed from X-ray diffraction patterns and Raman spectra at room temperature in all of these doped samples. Curie transition temperatures in doped LaMnO3 bulk samples were around 250K, which are much higher than the ideal value (˜140 K) in undoped samples. The increase in the magnetic transition temperatures can be related to non-stoichiometry and cation vacancies created due to higher valence substitutions for the univalent La1+ ions.

Effect of Al and Ti substitution on the structural and magnetotransport properties of Lanthanum-Strontium manganite

NASA Astrophysics Data System (ADS)

Jadav, G. D.; Kanjariya, P. V.; Chavda, S. K.; Bhalodia, J. A.

2018-05-01

Manganite systems have been of considerable interest in the recent past due to their potential to operate in wide property range and also to serve as effective magnetic sensing and storing devices. We report a novel hybrid method, by which La0.7Sr0.3Mn1-xAxO3 (A = Al and Ti, x = 0.00 and 0.06) samples were synthesized at temperature 1100 °C. La0.7Sr0.3MnO3 was selected as a parent material because it has metal to insulator transition near to room temperature. The XRD confirms that all the samples were in single phase (with no detectable secondary phases) having a rhombohedral structure in hexagonal lattice having a space group R3¯c. Unit cell volume is affected by Al+3 and Ti+4 ions and this structural variation slows down the electron transfer through the Mn+3-O-2-Mn+4 network seriously. EDAX analysis shows that the weight percentage of prepared samples matches with the calculated weight percentage of all the samples. Scanning electron microscopy shows that each sample has fine and clear grain boundaries (GBs). Metal-insulator transition (TMI) was increased from 230 K to 275 K in Ti+4 doped sample while TMI remain unchanged in Al+3 substituted sample under the 8 T applied magnetic field. As a positive effect, enhancement in MR % was observed at room temperature. These results prove that Al and Ti substitution at Mn site enhances the various properties of this manganite system. These properties are important for application point of view.

Microstructural, Magnetic, and Optical Properties of Pr-Doped Perovskite Manganite La0.67Ca0.33MnO3 Nanoparticles Synthesized via Sol-Gel Process.

PubMed

Xia, Weiren; Wu, Heng; Xue, Piaojie; Zhu, Xinhua

2018-05-04

We report on microstructural, magnetic, and optical properties of Pr-doped perovskite manganite (La 1 - x Pr x ) 0.67 Ca 0.33 MnO 3 (LPCMO, x = 0.0-0.5) nanoparticles synthesized via sol-gel process. Structural characterizations (X-ray and electron diffraction patterns, (high resolution) TEM images) provide information regarding the phase formation and the single-crystalline nature of the LPCMO systems. X-ray and electron diffraction patterns reveal that all the LPCMO samples crystallize in perovskite crystallography with an orthorhombic structure (Pnma space group), where the MnO 6 octahedron is elongated along the b axis due to the Jahn-Teller effect. That is confirmed by Raman spectra. Crystallite sizes and grain sizes were calculated from XRD and TEM respectively, and the lattice fringes resolved in the high-resolution TEM images of individual LPCMO nanoparticle confirmed its single-crystalline nature. FTIR spectra identify the characteristic Mn-O bond stretching vibration mode near 600 cm - 1 , which shifts towards high wavenumbers with increasing post-annealing temperature or Pr-doping concentration, resulting in further distortion of the MnO 6 octahedron. XPS revealed dual oxidation states of Mn 3+ and Mn 4+ in the LPCMO nanoparticles. UV-vis absorption spectra confirm the semiconducting nature of the LPCMO nanoparticles with optical bandgaps of 2.55-2.71 eV. Magnetic measurements as a function of temperature and magnetic field at field cooling and zero-field cooling modes, provided a Curie temperature around 230 K, saturation magnetization of about 81 emu/g, and coercive field of 390 Oe at 10 K. Such magnetic properties and the semiconducting nature of the LPCMO nanoparticles will make them as suitable candidate for magnetic semiconductor spintronics.

Electronic structure, optical and magnetic studies of PLD-grown (Mn, P)-doped ZnO nanocolumns at room temperature

NASA Astrophysics Data System (ADS)

Phan, The-Long; Ho, T. A.; Dang, N. T.; Nguyen, Manh Cuong; Dao, Van-Duong

2017-07-01

We prepared well-aligned Zn1-x Mn x O:yP nanocolumns (x  =  0-0.02, and y  =  0 and 1 mol%) on SiO2/Si(0 0 1) substrates by using pulsed laser deposition (PLD) and then investigated their electronic structure and optical and magnetic properties at room temperature. The analyses of x-ray photoelectron and x-ray absorption fine structure spectra revealed Mn2+ and/or P ions existing in nanocolumns, where Mn2+ ions are situated in the Zn2+ site of the ZnO-wurtzite structure. Although the incorporation of Mn2+ and/or P ions did not form secondary phases, as confirmed by x-ray and electron diffraction patterns, more lattice defects were created, and consequently changed the band-gap energy as well as the electron-phonon interactions in the nanocolumns. Magnetization versus magnetic-field measurements revealed that all the samples exhibited FM order. In particular, the (Mn, P) co-doping with x  =  0.02 and y  =  1 remarkably enhanced the magnetic moment up to 2.92 µ B/Mn. Based on the results obtained from analyzing the electronic structures, UV-Vis absorption and resonant Raman scattering spectra, and theoretical calculations, we believe that the enhancement of the FM order in (Mn, P)-doped ZnO nanocolumns is due to exchange interactions taking place between vacancy-mediated Mn2+ ions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanjeewa, Liurukara D.; McMillen, Colin D.; McGuire, Michael A.

We synthesized manganese vanadate fluorides using high-temperature hydrothermal techniques with BaF 2 as a mineralizer. Ba 3Mn 2(V 2O 7) 2F 2 crystallizes in space group C2/c and consists of dimers built from edge-sharing MnO 4F 2 trigonal prisms with linking V 2O 7 groups. Ba 7Mn 8O 2(VO 4) 2F 23 crystallizes in space group Cmmm, with a manganese oxyfluoride network built from edge- and corner-sharing Mn 2+/3+(O,F) 6 octahedra. The resulting octahedra form alternating Mn 2+ and Mn 2+/3+ layers separated by VO 4 tetrahedra. This latter compound exhibits a canted antiferromagnetic order below TN = 25 K.

Electrical Characteristics of MnO2 Doped Bismuth Borate Glass Systems

NASA Astrophysics Data System (ADS)

Nissar, Umair; Ahmad, Javed; Rana, Anwar Manzoor; Bukhari, S. H.; Jamil, M. T.; Khan, J. Alam; Shakeel, R.; Nadeem, M. Y.

2018-02-01

Transparent glasses have a large number of applications in the industry of electronics as well as optical devices. xMnO2-(25- x) Bi2O3-75H3BO3 (0 ≤ x ≤ 1.5 mol.%) transparent glasses have been prepared via melt-quench technique and characterized using dc electrical measurements, and by analyzing x-ray diffraction and Fourier transform infrared (FTIR) spectra. These characteristics were examined to understand the role of modifier oxides, i.e., Bi2O3 and MnO2 in the B2O3 glass network. Adding MnO2 into a glass network causes structural changes, which are responsible for any variations in electrical characteristics of bismuth borate glasses. Manganese bismuth borate glasses (MBBG) show Ohmic conduction at low fields; however, glasses with higher manganese content seem to conduct through bulk limited Poole-Frenkel mechanism. FTIR spectroscopy analyses depict the presence of BO3 and BO4 groups along with B-O-B and Bi-O-Bi bonding vibrations. Glasses with higher MnO2 content also show Mn-O bond vibrations. The reduction of BO4 groups and increase of BO3 units lead to the formation of non-bridging oxygens (NBOs) which are responsible for the variations in the electrical properties of these glasses.

Transport and magnetic properties of Fe doped CaMnO3

NASA Astrophysics Data System (ADS)

Neetika; Das, A.; Dhiman, I.; Nigam, A. K.; Yadav, A. K.; Bhattacharyya, D.; Meena, S. S.

2012-12-01

The structural, transport, and magnetic properties of CaMn1-xFexO3-δ (0.0 ≤ x ≤ 0.3) have been studied by using resistivity, magnetization, and neutron powder diffraction techniques. The compounds are found to be isostructural and crystallize in GdFeO3-type orthorhombic structure (space group Pnma). With Fe doping, no structural change is observed. Mössbauer and paramagnetic susceptibility measurements show that Fe substitutes in 4+ valence state, and XANES measurements indicate the presence of mixed valence state of Mn. The compounds exhibit insulating behavior in the studied temperature range. The temperature dependence of resistivity is found to be described by small polaron model for x = 0 and variable range hopping model for x = 0.1. For higher x values, it follows a parallel combination resistance model. A small reduction in TN from 120 K to 100 K with increase in x is found. The magnetic structure changes from Gz-type collinear antiferromagnetic (AFM) structure for x = 0.0 to canted AFM structure GZFY-type for Fe doped compounds. The AFM component of the moment progressively decreases with x while FM component exhibits a maximum at x = 0.2.

Cation substitution in synthetic meridianiite (MgSO4·11H2O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

NASA Astrophysics Data System (ADS)

Fortes, A. Dominic; Browning, Frank; Wood, Ian G.

2012-05-01

Meridianiite, MgSO4·11H2O, is the most highly hydrated phase in the binary MgSO4-H2O system. Lower hydrates in the MgSO4-H2O system have end-member analogues containing alternative divalent metal cations (Ni2+, Zn2+, Mn2+, Cu2+, Fe2+, and Co2+) and exhibit extensive solid solution with MgSO4 and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO4 solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO4 forms an undecahydrate; ZnSO4 forms an orthorhombic heptahydrate (synthetic goslarite), MnSO4, FeSO4, and CoSO4 form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO4 crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO4 forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) Å3, is consistent with it being an octahydrate, NiSO4·8H2O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co2+ or Mn2+, 20-30 mol. % Ni2+ or Zn2+, but less than 10 mol. % of Cu2+ or Fe2+. In three of the systems we examined, an `intermediate' phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO4, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg0.5Cu0.5)SO4·7H2O)]. In the NiSO4- and ZnSO4-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO4- and the FeSO4-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P21/ c with Z = 4. The unit-cell volume, V = 1,176.59(5) Å3, is consistent with it being an enneahydrate [i.e. (Mg0.5Ni0.5)SO4·9H2O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) Å3, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) Å3. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.

Optical Experiments With Manganese Doped Yttrium Orthoaluminate, a Potential Material for Holographic Recording and Data Storage

NASA Technical Reports Server (NTRS)

Warren, Matthew E.; Loutts, George

1998-01-01

The YAlO3 host crystal has a distorted perovskite structure that belongs to the orthorhombic centrosymmetric Pbnm space group. The cationic sites in the structure available for Mn substitution are the relatively large strongly distorted YO12 polyhedral (Y3+ ionic radius R(sub Y) = 1.02 A) and the smaller nearly ideal AlO6 octahedra R(sub Al) = 0.53 A). Manganese may enter YAlO3 in the form of Mn2+ ions (R(sub Mn)= 0.96 A), substituting most likely Y3+ ions, and Mn3+ ions (R(sub Mn) = 0.65 A) or Mn4+ ions (R(sub Mn) = 0.53 A) substituting Al3+ ions. The latter substitution is most probable because of dimensional parameters. Point defects, which are common in YAl03, may provide the charge compensation required for substitution.

Synthesis, structure and magnetic properties of nanostructured La1-xAxFe0.5Mn0.5O3 (A = Ca, Sr and Pb; x = 0 & 0.25) perovskites

NASA Astrophysics Data System (ADS)

Hossain, Aslam; Ghosh, Debamalya; Dutta, Uma; Walke, Pravin S.; Mordvinova, Natalia E.; Lebedev, Oleg I.; Sinha, Bhavesh; Pal, Kamalesh; Gayen, Arup; Kundu, Asish K.; Seikh, Md. Motin

2017-12-01

The effect of hole doping on magnetic properties of LaFe0.5Mn0.5O3 have been investigated. All the ceramics samples La1-xAxFe0.5Mn0.5O3 (A = Ca, Sr and Pb; x = 0 & 0.25) were synthesized at 500 °C by sol-gel method and the particles size were found to be in nanodimension. The samples were characterized by X-ray and electron diffraction, HRTEM and both dc and ac-magnetization measurements. The X-ray and electron diffraction patterns were indexed by cubic Pm-3m space group. The particle size of the LaFe0.5Mn0.5O3 is ∼100 nm, whereas the Pb-doped sample is ∼50 nm and for Ca or Sr doped samples the size is ∼10-30 nm. Both dc and ac-susceptibility measurements suggest that the effect of hole doping and A-site cationic radius in LaFe0.5Mn0.5O3 have no significant role on magnetic properties. However, the particle size plays an important role on magnetic property due to the development of surface ferromagnetic cluster at nanoscale. The competing interactions lead to magnetic phase separation where local ferromagnetic clusters coexist within the antiferromagentic matrix in all the samples.

Enhancement in electrical and magnetic properties with Ti-doping in Bi0.5La0.5Fe0.5Mn0.5O3

NASA Astrophysics Data System (ADS)

Singh, Rahul; Gupta, Prince Kumar; Kumar, Shiv; Joshi, Amish G.; Ghosh, A. K.; Patil, S.; Chatterjee, Sandip

2017-04-01

In this investigation, we have synthesized Bi0.5La0.5Fe0.5Mn0.5-xTixO3 (where x = 0 and 0.05) samples. The Rietveld refinement of X-ray diffraction (XRD) patterns shows that the systems crystallize in the orthorhombic phase with the Pnma space group. The observed Raman modes support the XRD results. The appearance of prominent A1-3 and weak E-2 modes in Bi0.5La0.5Fe0.5Mn0.45Ti0.05O3 indicates the presence of chemically more active Bi-O covalent bonds. Ferromagnetism of Bi0.5La0.5Fe0.5Mn0.5O3 is enhanced by Ti doping at the Mn-site, indicating that these particular samples might be interesting for device applications.

Comparative study on the physical properties of transition metal-doped (Co, Ni, Fe, and Mn) ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Azab, A. A.; Ateia, Ebtesam E.; Esmail, S. A.

2018-07-01

Nano-crystalline of TM-doped ZnO with general formula Zn0.97TM0.03O (TM: Mn, Fe, Co, and Ni) was prepared using sol-gel method. The dependence of crystal structure, morphology, and optical and magnetic properties on the type of transition metals was investigated. The XRD investigation of pure and TM-doped ZnO nanoparticles samples confirms the formation of single-phase hexagonal wurtzite structure. The estimated crystallite sizes are found in the range of 17 and 38 nm for the doped and pure samples, respectively. The obtained data suggest that the dopant type plays a vital role in the physical properties of the investigated samples. The optical band-gap energy Eg has been calculated from near infrared (NIR) and visible (VIS) reflectance spectra using the Kubelka-Munk function. Minimum value of 2.398 eV and maximum one of 3.29 eV were obtained for Manganese-doped ZnO and pure ZnO, respectively. The analysis of XRD and VSM of the samples confirms that the observed room-temperature (RT) ferromagnetism can be attributed to an intrinsic property of doped material sample and not due to formation of any secondary phase. The magnetic results show that Mn is the most effective dopant for producing ferromagnetism in nanoparticles of ZnO.

Tuning the dead-layer behavior of La{sub 0.67}Sr{sub 0.33}MnO{sub 3}/SrTiO{sub 3} via interfacial engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, R.; Xu, H. C.; Xia, M.

The dead-layer behavior, deterioration of the bulk properties in near-interface layers, restricts the applications of many oxide heterostructures. We present the systematic study of the dead-layer in La{sub 0.67}Sr{sub 0.33}MnO{sub 3}/SrTiO{sub 3} grown by ozone-assisted molecular beam epitaxy. Dead-layer behavior is systematically tuned by varying the interfacial doping, while unchanged with varied doping at any other atomic layers. In situ photoemission and low energy electron diffraction measurements suggest intrinsic oxygen vacancies at the surface of ultra-thin La{sub 0.67}Sr{sub 0.33}MnO{sub 3}, which are more concentrated in thinner films. Our results show correlation between interfacial doping, oxygen vacancies, and the dead-layer, whichmore » can be explained by a simplified electrostatic model.« less

A novel red phosphor of seven-coordinated Mn4+ ion-doped tridecafluorodizirconate Na5Zr2F13 for warm WLEDs.

PubMed

Xi, Luqing; Pan, Yuexiao; Huang, Shaoming; Lian, Hongzhou; Lin, Jun

2018-04-24

Herein, a novel red phosphor based on seven-coordinated Mn4+ ion-doped tridecafluorodizirconate, Na5Zr2F13 (NZF), has been synthesized by stirring a mixture of K2MnF6, NaF, and H2ZrF6 at room temperature. The crystal structure and morphology of the as-obtained phosphor NZF:Mn have been determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The composition and distribution of Mn4+ ions in NZF have been confirmed by energy-dispersive spectroscopy (EDS) and element mapping via transmission electron microscopy (TEM). The phosphor NZF:Mn exhibits a strong zero phonon line (ZPL) at 616 nm under excitation of blue light from a GaN light-emitting diode (LED) chip; this is attributed to the low symmetry of Mn4+ ions occupied in a seven-coordinated environment. The luminescence intensity of NZF:Mn has been optimized by controlling the synthesis procedure and synthetic parameters. The luminescence mechanism of the red phosphor NZF:Mn has been investigated according to the detailed experimental results. A warm white light has been produced by a WLED fabricated with the red phosphor NZF:Mn and the commercial yellow phosphor Y3Al5O12:Ce3+ (YAG:Ce) on a GaN LED chip.

The development of a wide field UV imager for planetary space missions

NASA Astrophysics Data System (ADS)

Molyneux, Philippa Mary

2012-03-01

This thesis describes experimental work carried out on bilayer manganites with the general composition R{2-2x}A{1+2x}Mn2O7, where R is a trivalent rare earth cation and A is a divalent alkaline-earth cation. Experiments have been carried out primarily using Scanning Tunnelling Microscopy (STM) and Spectroscopy (STS); bulk electrical transport, MPMS and LEED measurements have also been made. The primary results are obtained from single crystal samples of PrSr2Mn2O7. This compound provides a surface suitable for STM study when cleaved at low temperature in ultra-high vacuum: atomic resolution can be readily achieved. The expected square lattice is observed, together with a larger scale surface modulation which is not presently explained. In some areas of the PrSr2Mn2O7 surface a population of adatoms and surface vacancies is observed. STS data indicate that adatoms carry a negative charge compared to the rest of the surface, and vacancies a positive charge: the adatoms and vacancies are interpreted as oxygen adatoms and oxygen vacancies. A detailed study is made of the oxygen adatoms and vacancies: this is believed to be the firrst such study made on a manganite surface. Oxygen adatoms on the PrSr2Mn2O7 surface are found to be mobile: hopping and adatom-vacancy recombination are observed. Additional results are reported on the layered manganite compound La{2-2x}Sr{1+2x}Mn2O7 at a range of cation doping x. For the LaSr2Mn2O7 compound (x = 0.5) spectroscopic variation has been identified in a variable-temperature STS survey. This indicates the coexistence of two surface electronic phases, possibly the charge ordered and antiferromagnetic phases.

Electrical and magnetic properties of La0.67Ba0.33Mn1- x (Me) x O3 perovskite manganites: case of manganese substituted by trivalent (Me = Cr) and tetravalent (Me = Ti) elements

NASA Astrophysics Data System (ADS)

Oumezzine, Marwène; Peña, Octavio; Kallel, Sami; Kallel, Nabil; Guizouarn, Thierry; Gouttefangeas, Francis; Oumezzine, Mohamed

2014-03-01

The effects of non-magnetic Ti4+ substitution on the structural, electrical and magnetic properties of La0.67Ba0.33Mn1- x Ti x O3 (0≤ x≤0.1) are investigated and compared to those existing in La0.67Ba0.33Mn1- x Cr x O3 (magnetic Cr3+). The structural refinement by the Rietveld method revealed that Ti-doped samples crystallize in the cubic lattice with space group , while samples with Cr crystallize in the hexagonal setting of the rhombohedral space group for identical contents of dopant. The most relevant structural features are an increase of the lattice parameters, of the cell volume and of the inter-ionic distances with increasing Ti doping level. Both series of samples show a decrease of the paramagnetic-ferromagnetic transition temperature when the amount of chromium or titanium increases. Transport measurements show that when increasing the metal doping, the resistivity increases whereas the metallic behavior of the parent compound La0.67Ba0.33MnO3 is destroyed. For a substitution higher than 5 at.% of Ti and 10 at.% of Cr, the samples exhibit a semiconducting behavior in the whole range of temperature, for which the electronic transport can be explained by variable range hopping and/or small polaron hopping models.

Na-doped La0.7Ca0.3MnO3 compounds exhibiting a large magnetocaloric effect near room temperature

NASA Astrophysics Data System (ADS)

Chi Linh, Dinh; Thi Ha, Nguyen; Huu Duc, Nguyen; Giang Nam, Le Huu; Bau, Le Viet; Manh An, Nguyen; Yu, Seong-Cho; Dang Thanh, Tran

2018-03-01

In this work, we have investigated the magnetic properties and the magnetocaloric effect of La0.7-xNaxCa0.3MnO3 compounds, which were prepared by a conventional solid-state reaction technique. The Rietveld refinement results suggested that the samples are single phase belonging to an orthorhombic structure (space group Pnma). Analyzing temperature dependence of magnetization M(T) revealed that the Curie temperature (TC) increases with increasing Na content (x). Their TC value is found to be 260-298 K for x=0.0-0.1, respectively. Base on M(T) data measured at different applied magnetic fields (H), temperature dependence of magnetic entropy change ΔSm(T) data for all the samples was calculated by using a phenomenological model. In the vicinity of TC, -ΔSm(T) curve reaches a maximum value (denoted as |ΔSmax|), which gradually increases with increasing H. Under 12 kOe, the value of |ΔSmax| is in a range of 1.47-5.19 J/kg K corresponding to the relative cooling power RCP=57.12-75.88 J/kg. Applied the universal master curve method for the magnetic entropy change, we concluded that Na-doped in La0.7-xNaxCa0.3MnO3 compounds leads to modification the nature of the magnetic phase transition from the first- to the second-order.

Mn1.4Co1.4Cu0.2O4 spinel protective coating on ferritic stainless steels for solid oxide fuel cell interconnect applications

NASA Astrophysics Data System (ADS)

Chen, Guoyi; Xin, Xianshuang; Luo, Ting; Liu, Leimin; Zhou, Yuchun; Yuan, Chun; Lin, Chucheng; Zhan, Zhongliang; Wang, Shaorong

2015-03-01

In an attempt to reduce the oxidation and Cr evaporation rates of solid oxide fuel cells (SOFCs), Mn1.4Co1.4Cu0.2O4 spinel coating is developed on the Crofer22 APU ferritic stainless steel substrate by a powder reduction technique. Doping of Cu into Mn-Co spinels improves electrical conductivity as well as thermal expansion match with the Crofer22 APU interconnect. Good adhesion between the coating and the alloy substrate is achieved by the reactive sintering process using the reduced powders. Long-term isothermal oxidation experiment and area specific resistance (ASR) measurement are investigated. The ASR is less than 4 mΩ cm2 even though the coated alloy undergoes oxidation at 800 °C for 530 h and four thermal cycles from 800 °C to room temperature. The Mn1.4Co1.4Cu0.2O4 spinel coatings demonstrate excellent anti-oxidation performance and long-term stability. It exhibits a promising prospect for the practical application of SOFC alloy interconnect.

Ferromagnetism induced by oxygen-vacancy complex in (Mn, in) codoped ZnO

NASA Astrophysics Data System (ADS)

Wu, Kongping; Gu, Shulin; Tang, Kun; Zhu, Shunming; Zhou, Mengran; Huang, Yourui; Xu, Mingxiang; Zhang, Rong; Zheng, Youdou

2012-07-01

Mn doped Zinc oxide (ZnO) thin films were prepared by metal organic chemical vapor deposition (MOCVD) technique. Structural characterizations by X-ray diffraction technique (XRD) and photoluminescence (PL) indicate the crystal quality of ZnO films. PL and Raman show a large fraction of oxygen vacancies (VO2+) are generated by vacuum annealed the film. The enhancement of ferromagnetism in post-annealed (Mn, In) codoped ZnO could result from VO2+ incorporation. The effect of VO2+ on the magnetic properties of (Mn, In) codoped ZnO has been studied by first-principles calculations. It is found that only In donor cannot induce ferromagnetism (FM) in Mn-doped ZnO. Besides, the presence of VO2+ makes the Mn empty 3d-t2g minority state broadened, and a t2g-VO2+ hybrid level at the conduction band minimum forms. The presence of VO2+ can lead to strong ferromagnetic coupling with the nearest neighboring Mn cation by BMP model based on defects reveal that the ferromagnetic exchange is mediated by the donor impurity state, which mainly consists of Mn 3d electrons trapped in oxygen vacancies.

Outstanding supercapacitive properties of Mn-doped TiO2 micro/nanostructure porous film prepared by anodization method

PubMed Central

Ning, Xuewen; Wang, Xixin; Yu, Xiaofei; Zhao, Jianling; Wang, Mingli; Li, Haoran; Yang, Yang

2016-01-01

Mn-doped TiO2 micro/nanostructure porous film was prepared by anodizing a Ti-Mn alloy. The film annealed at 300 °C yields the highest areal capacitance of 1451.3 mF/cm2 at a current density of 3 mA/cm2 when used as a high-performance supercapacitor electrode. Areal capacitance retention is 63.7% when the current density increases from 3 to 20 mA/cm2, and the capacitance retention is 88.1% after 5,000 cycles. The superior areal capacitance of the porous film is derived from the brush-like metal substrate, which could greatly increase the contact area, improve the charge transport ability at the oxide layer/metal substrate interface, and thereby significantly enhance the electrochemical activities toward high performance energy storage. Additionally, the effects of manganese content and specific surface area of the porous film on the supercapacitive performance were also investigated in this work. PMID:26940546

The influence of manganese-cobalt oxide/graphene on reducing fire hazards of poly(butylene terephthalate).

PubMed

Wang, Dong; Zhang, Qiangjun; Zhou, Keqing; Yang, Wei; Hu, Yuan; Gong, Xinglong

2014-08-15

By means of direct nucleation and growth on the surface of graphene and element doping of cobalt oxide (Co3O4) nano-particles, manganese-cobalt oxide/graphene hybrids (MnCo2O4-GNS) were synthesized to reduce fire hazards of poly(butylene terephthalate) (PBT). The structure, elemental composition and morphology of the obtained hybrids were surveyed by X-ray diffraction, X-ray photoelectron spectrometer and transmission electron microscopy, respectively. Thermogravimetric analysis was applied to simulate and study the influence of MnCo2O4-GNS hybrids on thermal degradation of PBT during combustion. The fire hazards of PBT and its composites were assessed by the cone calorimeter. The cone test results had showed that peak HRR and SPR values of MnCo2O4-GNS/PBT composites were lower than that of pure PBT and Co3O4-GNS/PBT composites. Furthermore, the incorporation of MnCo2O4-GNS hybrids gave rise to apparent decrease of pyrolysis products containing aromatic compounds, carbonyl compounds, carbon monoxide and carbon dioxide, attributed to combined impact of physical barrier for graphene and cat O4 for organic volatiles and carbon monoxide. Copyright © 2014 Elsevier B.V. All rights reserved.

Charge versus orbital-occupancy ordering in manganites

NASA Astrophysics Data System (ADS)

Luo, Weidong; Varela, Maria; Tao, Jing; Pennycook, Stephen J.; Pantelides, Sokrates T.

2006-03-01

It is generally assumed that density-functional theory (DFT) in the local-spin-density approximation (LSDA) or the generalized- gradient approximation (GGA) is not adequate to describe mixed- valence manganites. Here we report benchmark DFT/GGA calculations for the ground-state structural, electronic and magnetic properties for both undoped and doped CaMnO3 and find the results to be in excellent agreement with available data, including new atomic-resolution Z-contrast imaging and electron-energy loss spectra. More specifically, we found that the DFT results predict two inequivalent Mn atoms in both 0.33 and 0.5 electron-doped CaMnO3, in agreement with experimental evidence of Mn^+3/Mn^+4 oxidation state ordering. The inequivalent Mn atoms are marked by their distinctive orbital occupancies, dissimilar local Jahn-Teller distortion and different magnetic moments from DFT calculations. We also show that the spherically integrated charges associated with the two inequivalent Mn atoms are the same, and they are actually the same as in the Mn metal. This charge neutrality with different orbital occupancies is the result of self-consistency and atomic relaxations in the crystal. We conclude that DFT without additional correlations can account for the observed properties of oxidation-state ordering in this system. The impact of the results on other mixed-valence systems will be discussed.

Observation of magnetization reversal behavior in Sm0.9Gd0.1Cr0.85Mn0.15O3 orthochromites

NASA Astrophysics Data System (ADS)

Panwar, Neeraj; Joby, Jostin P.; Kumar, Surendra; Coondoo, Indrani; Vasundhara, M.; Kumar, Nitu; Palai, Ratnakar; Singhal, Rahul; Katiyar, Ram S.

2018-05-01

Impact of co-doping (Gd and Mn) on the magnetic properties has been systematically investigated in SmCrO3 compound. For the synthesized compound Sm0.9Gd0.1Cr0.85Mn0.15O3 (SGCMO), below the Neel transition temperature and under low applied magnetic field, temperature induced magnetization reversal at 105 K (crossover temperature) was noticed in the field cooled magnetization curve. Magnetization reversal attained maximum value of -1.03 emu/g at 17 K where spin reorientation occurred. The magnetization reversal disappeared under higher applied field. From the M-H plots an enhancement in the magnetization was observed due to Gd doping. Magnetocaloric effect at low temperatures measured through the magnetic entropy change was found sixteen times higher for this compound as compared to pristine SmCrO3 and twice to that of SmCr0.85Mn0.15O3 compound. The study reveals the importance of co-doping in tailoring the magnetic properties of rare-earth chromites.

The effects of annealing temperature on the in-field Jc and surface pinning in silicone oil doped MgB2 bulks and wires

NASA Astrophysics Data System (ADS)

Hossain, M. S. A.; Motaman, A.; Çiçek, Ö.; Ağıl, H.; Ertekin, E.; Gencer, A.; Wang, X. L.; Dou, S. X.

2012-12-01

The effects of sintering temperature on the lattice parameters, full width at half maximum (FWHM), strain, critical temperature (Tc), critical current density (Jc), irreversibility field (Hirr), upper critical field (Hc2), and resistivity (ρ) of 10 wt.% silicone oil doped MgB2 bulk and wire samples are investigated in state of the art by this article. The a-lattice parameter of the silicone oil doped samples which were sintered at different temperatures was drastically reduced from 3.0864 Å to 3.0745 Å, compared to the un-doped samples, which indicates the substitution of the carbon (C) into the boron sites. It was found that sintered samples at the low temperature of 600 °C shows more lattice distortion by more C-substitution and higher strain, lower Tc, higher impurity scattering, and enhancement of both magnetic Jc and Hc2, compared to those sintered samples at high temperatures. The flux pinning mechanism has been analyzed based on the extended normalized pinning force density fp = Fp/Fp,max scaled with b = B/Bmax. Results show that surface pinning is the dominant pinning mechanism for the doped sample sintered at the low temperature of 600 °C, while point pinning is dominant for the un-doped sample. The powder in tube (PIT) MgB2 wire was also fabricated by using of this liquid doping and found that both transport Jc and n-factor increased which proves this cheap and abundant silicone oil doping can be a good candidate for industrial application.

Optical and Structural Properties of Zn2TiO4:Mn2+

NASA Astrophysics Data System (ADS)

Sosman, L. P.; López, A.; Camara, A. R.; Pedro, S. S.; Carvalho, I. C. S.; Cella, N.

2017-12-01

Polycrystalline Zn2TiO4 samples with Mn2+ doping level of 0%, 0.1%, 1.0%, and 5.0% have been produced by conventional solid-state method and their optical and structural properties investigated. Rietveld refinement of x-ray diffraction patterns revealed the formed phases and the crystallographic parameters. The chemical composition was obtained by x-ray fluorescence measurements. The optical properties were studied by photoluminescence, excitation, reflectance, and photoacoustic spectroscopy. All measurements were performed at room temperature. The photoluminescence spectrum of the pure sample (0% Mn2+) showed a band in the red region associated with Zn2TiO4, while the sample with 0.1% Mn2+ exhibited two bands, in the green and red spectral regions, assigned to Mn2+ ions at tetrahedral and octahedral sites. No emission was observed for the samples with 1.0% or 5.0% Mn2+. The excitation results for the sample with 0.1% Mn2+ ions showed characteristic peaks of Mn2+ transitions. Tanabe-Sugano theory was used to obtain the crystal field Dq, B, and C Racah parameters from the energy peak positions in the excitation spectrum of the sample with 0.1% Mn2+. Photoacoustic measurements revealed a broad band, characteristic of semiconductor materials, hiding the Mn2+ transitions.

Electrical characterization of Mn doped-(Ba{sub 0.3}Sr{sub 0.7})Mn{sub x}(Ti{sub 0.9}Zr{sub 0.1}){sub 1-x}O{sub 3} ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahmood, A.; Materials Research Laboratory, Institute of Physics & Electronics, University of Peshawar, 25120; Department of Engineering Materials, University of Sheffield, Sheffield S1 3JD

2015-12-15

Highlights: • Solid state processing of the (Ba{sub 0.3}Sr{sub 0.7})Mn{sub x}(Ti{sub 0.9}Zr{sub 0.1}){sub 1−x}O{sub 3} ceramics. • Mn incorporated on the Ti-site into the host lattice of (Ba{sub 0.3}Sr{sub 0.7})Mn{sub x}(Ti{sub 0.9}Zr{sub 0.1}){sub 1−x}O{sub 3}. • NTCR behavior was observed in the sintered samples. - Abstract: (Ba{sub 0.3}Sr{sub 0.7})Mn{sub x}(Ti{sub 0.9}Zr{sub 0.1}){sub 1-x}O{sub 3} (x = 0.00, 0.013, 0.015 and 0.05) ceramics were prepared by solid state sintering route at the 1500 °C for 6 h in air. Effect of Mn substitution on the structure of Ba{sub 0.3}Sr{sub 0.7}(Ti0{sub .9}Zr{sub 0.1}){sub 1−x}O{sub 3} perovskite was investigated systematically. Dielectric and impedancemore » spectroscopic studies were conducted to understand the electronic microstructure of the Ba{sub 0.3}Sr{sub 0.7}(Ti0{sub .9}Zr{sub 0.1}){sub 1−x}O{sub 3} ceramics. Sample with x = 0.05 showed the highest dielectric constant (ϵ{sub r} = 1826) and low dielectric loss (tanδ = 0.001) at 10 kHz, around the room temperature, while the sample with x = 0.00 showed good microwave (MW) dielectric properties (Qf{sub o} = 838 and ϵ{sub r} = 550). The impedance spectroscopic analysis confirmed the electrical homogeneity of the samples with x = 0.013, 0.015 and 0.05, where grain boundaries dominated the conduction mechanism. Similarly, the sample with x = 0.00 was found to possess both grain boundary and bulk resistive contributions.« less

Control of electrochemical properties of nickel-rich layered cathode materials for lithium ion batteries by variation of the manganese to cobalt ratio

NASA Astrophysics Data System (ADS)

Sun, Ho-Hyun; Choi, Wonchang; Lee, Joong Kee; Oh, In-Hwan; Jung, Hun-Gi

2015-02-01

Various Ni-rich layered oxide cathodes (above 0.80 Ni content), such as LiNi1-y-zCoyAlzO2 (NCA), are used in electric vehicles (EVs) due to their high capacity (∼200 mAh g-1 for NCA). However, to improve cycle performance and thermal stability and to ensure longer and safer usage, numerous studies have investigated surface modification, coating, and doping of cathode materials. In this study, we have investigated the characteristics of Li[Ni0.85CoxMn0.15-x]O2 with various Mn to Co ratios (x = 0-0.15) synthesized by a coprecipitation method. The discharge capacities of the Li[Ni0.85CoxMn0.15-x]O2 cathodes are similar at around 206 mAh g-1 at room temperature and 213.8 mAh g-1 at 55 °C between 2.7 and 4.3 V at a 0.2C rate, while the cyclability, thermal stability, and rate capability of all samples differ according to the Mn and Co ratio. The Li[Ni0.85Co0.05Mn0.10]O2 cathode shows the most promising electrochemical properties under different conditions among the various cathodes evaluated; it displays a high rate capacity (approximately 163 mAh g-1 at 5C rate) at 25 °C and good thermal stability (main exothermic temperature of 233.7 °C and relatively low heat evolution of 857.3 J g-1).

Structural and electromagnetic characterization of Co-Mn doped Ni-Sn ferrites fabricated via micro-emulsion route

NASA Astrophysics Data System (ADS)

Ali, Rajjab; Azhar Khan, Muhammad; Manzoor, Alina; Shahid, Muhammad; Farooq Warsi, Muhammad

2017-11-01

Ni0.5Sn0.5CoxMnxFe2-2xO4 ferrites with x = 0.0-0.8 have been prepared by the micro-emulsion method, using CTAB as a surfactant material. X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR) and vibrational sample magnetometer (VSM) were used to investigate the effects of Co and Mn substitutions on cationic distribution, crystallite size, lattice constant, spectral, magnetic and dielectric properties. Lattice constant and crystallite size were found to increase from 7.4 to 9.25 Å and from 11.8 to 19.7 nm respectively with increasing substitution of Co and Mn ions. Saturation magnetization (MS) gradually increased from 20.5 to 47.6 emu/g with increase in the value of x. However, Coercivity increased from 152.7 to 462.4 Oe up to x = 0.4 and then it decreased thereafter. The dielectric constant, complex dielectric constant and tan loss (tanδ) were observed to decrease with increase in frequency, depicting the semiconductor behavior of the ferrites. Dc resistivity was observed to decrease considerably upon addition of Co and Mn content. The outcome for the tunable magnetic properties and achieved modification of the synthesized nanocrystallites may be chosen for tremendous applications; such as miniaturized memory devices that are based on the energy storage principles and capacitive components.

Improving soft magnetic properties of Mn-Zn ferrite by rare earth ions doping

NASA Astrophysics Data System (ADS)

Zhong, X. C.; Guo, X. J.; Zou, S. Y.; Yu, H. Y.; Liu, Z. W.; Zhang, Y. F.; Wang, K. X.

2018-04-01

Mn-Zn ferrites doped with different Sm2O3, Gd2O3, Ce2O3 or Y2O3 were prepared by traditional ceramic technology using industrial pre-sintered powders. A small amount of Sm2O3, Gd2O3, Ce2O3 or Y2O3 can significantly improve the microstructure and magnetic properties. The single spinel phase structure can be maintained with the doping amount up to 0.07 wt.%. A refined grain structure and uniform grain size distribution can be obtained by doping. For all rare earth oxides, a small amount of doping can significantly increase the permeability and reduce the coercivity and magnetic core loss. The optimized doping amount for Sm2O3 or Gd2O3 is 0.01 wt.%, while for Ce2O3 or Y2O3 is 0.03 wt.%. A further increase of the doping content will lead to reduced soft magnetic properties. The ferrite sample with 0.01 wt.% Sm2O3 exhibits the good magnetic properties with permeability, loss, and coercivity of 2586, 316 W/kg, and 24A/m, respectively, at 200 mT and 100 kHz. The present results indicate that rare earth doping can be suggested to be one of the effective ways to improve the performance of soft ferrites.

Synthesis and Electrochemical Property of LiMn2O4 Porous Hollow Nanofiber as Cathode for Lithium-Ion Batteries.

PubMed

Duan, Lianfeng; Zhang, Xueyu; Yue, Kaiqiang; Wu, Yue; Zhuang, Jian; Lü, Wei

2017-12-01

The LiMn 2 O 4 hollow nanofibers with a porous structure have been synthesized by modified electrospinning techniques and subsequent thermal treatment. The precursors were electrospun directly onto the fluorine-doped tin oxide (FTO) glass. The heating rate and FTO as substrate play key roles on preparing porous hollow nanofiber. As cathode materials for lithium-ion batteries (LIBs), LiMn 2 O 4 hollow nanofibers showed the high specific capacity of 125.9 mAh/g at 0.1 C and a stable cycling performance, 105.2 mAh/g after 400 cycles. This unique structure could relieve the structure expansion effectively and provide more reaction sites as well as shorten the diffusion path for Li + for improving electrochemical performance for LIBs.

Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Liu, Yisi; Li, Jie; Li, Wenzhang; Li, Yaomin; Chen, Qiyuan; Zhan, Faqi

2015-12-01

Spinel CoMn2O4 (CMO) nanoparticles grown on three-dimensional (3D) nitrogen-doped graphene areogel (NGA) is prepared by a facile two-step hydrothermal method. The NGA not only possesses the intrinsic property of graphene, but also has abundant pore conformations for supporting spinel metal oxide nanoparticles, thus would be suitable as a good electrocatalysts' support for oxygen reduction reaction (ORR). The structure, morphology, porous properties, and chemical composition of CMO/NGA are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O2-saturated 0.1 M KOH electrolyte. The CMO/NGA hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer than that of CMO and NGA, and its electrocatalytic performance is comparable with the commercial 20 wt.% Pt/C. Furthermore, it mainly favors a direct 4e- reaction pathway, and has excellent ethanol tolerance and high durability, which is attributed to the unique 3D crumpled porous nanostructure of NGA with large specific area and fast electron transport, and the synergic covalent coupling between the CoMn2O4 nanoparticles and NGA.

Crafting ferromagnetism in Mn-doped MgO surfaces with p-type defects

PubMed Central

Panigrahi, Puspamitra; Araujo, C Moyses; Hussen, Tanveer; Ahuja, Rajeev

2014-01-01

We have employed first-principles calculations based on density functional theory (DFT) to investigate the underlying physics of unusual magnetism in Mn-doped MgO surface. We have studied two distinct scenarios. In the first one, two Mn atoms are substitutionally added to the surface, occupying the Mg sites. Both are stabilized in the Mn valence state carrying a local moment of 4.3 having a high-spin configuration. The magnetic interaction between the local moments display a very short-ranged characteristic, decaying very quickly with distance, and having antiferromagnetic ordering lower in energy. The energetics analysis also indicates that the Mn ions prefer to stay close to each other with an oxygen atom bridging the local interaction. In the second scenario, we started exploring the effect of native defects on the magnetism by crafting both Mg and O vacancies, which are p- and n-type defects, respectively. It is found that the electrons and holes affect the magnetic interaction between Mn ions in a totally different manner. The n-type defect leads to very similar magnetism, with the AFM configuration being energetically preferred. However, in the presence of Mg vacancy, the situation is quite different. The Mn atoms are further oxidized, giving rise to mixed Mn(d) ionic states. As a consequence, the Mn atoms couple ferromagnetically, when placed in the close configuration, and the obtained electronic structure is coherent with the double-exchange type of magnetic interaction. To guarantee the robustness of our results, we have benchmarked our calculations with three distinct theory levels, namely DFT-GGA, DFT-GGA+U and DFT-hybrid functionals. On the surface, the Mg vacancy displays lower formation energy occurring at higher concentrations. Therefore, our model systems can be the basis to explain a number of controversial results regarding transition metal doped oxides. PMID:27877684

Study of As(III) and As(V) Oxoanion Adsorption onto Single and Mixed Ferrite and Hausmannite Nanomaterials

PubMed Central

Garcia, Sandra; Sardar, Saima; Maldonado, Stephanie; Garcia, Velia; Tamez, C.; Parsons, J. G.

2014-01-01

The removal of arsenic(III) and arsenic(V) from an aqueous solution through adsorption on to Fe3O4, MnFe2O4, 50% Mn substituted Fe3O4, 75% Mn substituted Fe3O4, and Mn3O4 nanomaterials was investigated. Characterization of the nanomaterials using XRD showed only pure phases for Mn3O4, MnFe2O4, and Fe3O4. The 50% and 75% substituted nanomaterials were found to be mixtures of Mn3O4 and Fe3O4. From batch studies the optimum binding pH of arsenic(III) and arsenic(V) to the nanomaterials was determined to be pH 3. The binding capacity for As(III) and As(VI) to the various nanomaterials was determined using Isotherm studies. The binding capacity of Fe3O4 was determined to be 17.1 mg/g for arsenic(III) and 7.0 mg/g for arsenic(V). The substitution of 25% Mn into the Fe3O4 lattice showed a slight increase in the binding capacity for As(III) and As(VI) to 23.8 mg/g and 7.9 mg/g, respectively. The 50% substituted showed the maximum binding capacity of 41.5 mg/g and 13.9 mg/g for arsenic(III) and arsenic(V). The 75% Mn substituted Fe3O4 capacities were 16.7 mg/g for arsenic(III) and 8.2 mg/g for arsenic(V). The binding capacity of the Mn3O4 was determined to be 13.5 mg/g for arsenic(III) and 7.5 mg/g for arsenic(V). In addition, interference studies on the effects of SO2−4, PO3−4, Cl−, and NO−3 investigated. All the interferences had very minimal effects on the As(III) and As(V) binding never fell below 20% even in the presence of 1000 ppm interfering ions. PMID:25097269

1H and 17O NMR relaxometric and computational study on macrocyclic Mn(II) complexes.

PubMed

Rolla, Gabriele A; Platas-Iglesias, Carlos; Botta, Mauro; Tei, Lorenzo; Helm, Lothar

2013-03-18

Herein we report a detailed 1H and 17O relaxometric investigation of Mn(II) complexes with cyclen-based ligands such as 2-(1,4,7,10-tetraazacyclododecan-1-yl)acetic acid (DO1A), 2,2'-(1,4,7,10-tetraazacyclododecane-1,4-diyl)diacetic acid (1,4-DO2A), 2,2'-(1,4,7,10-tetraazacyclododecane-1,7-diyl)diacetic acid (1,7-DO2A), and 2,2',2"-(1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetic acid (DO3A). The Mn(II) complex with the heptadentate ligand DO3A does not have inner sphere water molecules (q = 0), and therefore, the metal ion is most likely seven-coordinate. The hexadentate DO2A ligand has two isomeric forms: 1,7-DO2A and 1,4-DO2A. The Mn(II) complex with 1,7-DO2A is predominantly six-coordinate (q = 0). In aqueous solutions of [Mn(1,4-DO2A)], a species with one coordinated water molecule (q = 1) prevails largely, whereas a q = 0 form represents only about 10% of the overall population. The Mn(II) complex of the pentadentate ligand DO1A also contains a coordinated water molecule. DFT calculations (B3LYP model) are used to obtain information about the structure of this family of closely related complexes in solution, as well as to determine theoretically the 17O and 1H hyperfine coupling constants responsible for the scalar contribution to 17O and 1H NMR relaxation rates and 17O NMR chemical shifts. These calculations provide 17O A/ħ values of ca. 40 × 10(6) rad s(-1), in good agreement with experimental data. The [Mn(1,4-DO2A)(H2O)] complex is endowed with a relatively fast water exchange rate (k(ex)298 = 11.3 × 10(8) s(-1)) in comparison to the [Mn(EDTA)(H2O)]2- analogue (k(ex)298 = 4.7 × 10(8) s(-1)), but about 5 times lower than that of the [Mn(DO1A)(H2O)]+ complex (k(ex)298 = 60 × 10(8) s(-1)). The water exchange rate measured for the latter complex represents the highest water exchange rate ever measured for a Mn(II) complex.

In situ formation of oxygen vacancy in perovskite Sr0.95Ti0.8Nb0.1M0.1O3 (M = Mn, Cr) toward efficient carbon dioxide electrolysis

PubMed Central

Zhang, Jun; Xie, Kui; Wei, Haoshan; Qin, Qingqing; Qi, Wentao; Yang, Liming; Ruan, Cong; Wu, Yucheng

2014-01-01

In this work, redox-active Mn or Cr is introduced to the B site of redox stable perovskite Sr0.95Ti0.9Nb0.1O3.00 to create oxygen vacancies in situ after reduction for high-temperature CO2 electrolysis. Combined analysis using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis confirms the change of the chemical formula from oxidized Sr0.95Ti0.9Nb0.1O3.00 to reduced Sr0.95Ti0.9Nb0.1O2.90 for the bare sample. By contrast, a significant concentration of oxygen vacancy is additionally formed in situ for Mn- or Cr-doped samples by reducing the oxidized Sr0.95Ti0.8Nb0.1M0.1O3.00 (M = Mn, Cr) to Sr0.95Ti0.8Nb0.1M0.1O2.85. The ionic conductivities of the Mn- and Cr-doped titanate improve by approximately 2 times higher than bare titanate in an oxidizing atmosphere and 3–6 times higher in a reducing atmosphere at intermediate temperatures. A remarkable chemical accommodation of CO2 molecules is achieved on the surface of the reduced and doped titanate, and the chemical desorption temperature reaches a common carbonate decomposition temperature. The electrical properties of the cathode materials are investigated and correlated with the electrochemical performance of the composite electrodes. Direct CO2 electrolysis at composite cathodes is investigated in solid-oxide electrolyzers. The electrode polarizations and current efficiencies are observed to be significantly improved with the Mn- or Cr-doped titanate cathodes. PMID:25403738

Aluminum-Stabilized Magnesium Diboride Superconductors

NASA Astrophysics Data System (ADS)

Dou, S. X.; Collings, E. W.; Shcherbakova, O.; Shcherbakov, A.

2006-03-01

Use of aluminum as stabilizer and iron as reaction barrier for fabrication of MgB2 superconductor wires was studied. The MgB2/Fe/Al or SiC doped MgB2/Fe/Al composite wires were made using Mg+ 2 B powder or SiC doped Mg+2 B powder in Fe/Al tube technique. The composites were processed at 600°C to 650°C for 30 minutes to 3 hours to study the interaction between Fe and Al sheath and the formation of MgB2. No reaction between Fe and Al was found until annealing temperature at 620°C for 30 minutes. A thin layer of alloy, FeAl3 is formed for samples annealed at 620°C for 90 minutes and the reaction layer increases with increasing annealing temperature. Annealing at 650°C resulted in cracks in the Al sheath. Our results show that the Fe/Al sheathed wires achieved the same performance in magnetic and electrical properties as those using an all-Fe sheath. Comparing with the standard NbTi/Cu conductors, the MgB2/Fe/Al conductor having low structural mass, greater thermal conductivity and high efficient stabilization will make a tremendous difference especially for airborne, aerospace, and other applications when weight is important.

Structural, magnetic, and dielectric studies of the Aurivillius compounds SrBi{sub 5}Ti{sub 4}MnO{sub 18} and SrBi{sub 5}Ti{sub 4}Mn{sub 0.5}Co{sub 0.5}O{sub 18}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, B.; Yang, J., E-mail: jyang@issp.ac.cn; Zuo, X. Z.

We have successfully synthesized the Aurivillius compounds SrBi{sub 5}Ti{sub 4}MnO{sub 18} and SrBi{sub 5}Ti{sub 4}Mn{sub 0.5}Co{sub 0.5}O{sub 18} using a modified Pechini method. Both samples have an orthorhombic structure with the space group B2cb. The valence state of Mn is suggested to be +3 and the doped Co ions exist in the form of Co{sup 2+} and Co{sup 3+} based on the results of x-ray photoelectron spectroscopy. The sample SrBi{sub 5}Ti{sub 4}MnO{sub 18} exhibits a dominant paramagnetic state with the existence of superparamagnetic state as evidenced by the electron paramagnetic resonance results, whereas SrBi{sub 5}Ti{sub 4}Mn{sub 0.5}Co{sub 0.5}O{sub 18} undergoesmore » a ferrimagnetic transition at 161 K originating from the antiferromagnetic coupling of Co-based and Mn-based sublattices, and a ferromagnetic transition at 45 K arising from the Mn{sup 3+}-O-Co{sup 3+} (low spin) interaction. The sample SrBi{sub 5}Ti{sub 4}Mn{sub 0.5}Co{sub 0.5}O{sub 18} exhibits two dielectric anomalies. One corresponds to a relaxor-like dielectric relaxation which follows the Vogel-Fulcher function and the other dielectric relaxation obeys the Arrhenius law arising from the collective motion of oxygen vacancies. In addition, the sample SrBi{sub 5}Ti{sub 4}Mn{sub 0.5}Co{sub 0.5}O{sub 18} exhibits a magnetodielectric effect caused by the Maxwell-Wagner effect because of the conductivity of the sample. This is demonstrated by the fact that the activation energy in dielectric loss process is close to that for dc conductivity and the magnetodielectric effect is sensitive to the measured frequency.« less

Synthesis and characterization of spinel type high-power cathode materials Li MxMn2-x O4 (M=Ni, Co, Cr)

NASA Astrophysics Data System (ADS)

Yoon, Y. K.; Park, C. W.; Ahn, H. Y.; Kim, D. H.; Lee, Y. S.; Kim, J.

2007-05-01

The transition metal-doped spinel cathode materials, LiM0.5Mn1.5O4 (M=Ni. Co, Cr) were prepared by solid-state reaction. The structure and morphology of the samples were investigated by X-ray diffraction, Rietveld refinement and scanning electron microscopy (SEM). The diffraction peaks of all the samples corresponded to a single phase of cubic spinel structure with a space group Fd3m. Field-emission SEM shows octahedron like shapes and the primary particles size was between 500 nm and 2 μm. Oxidation states of Ni, Co and Cr were found to be 2+, 2+ and 3+ as revealed by X-ray photoelectron spectroscopy. During discharging, LiNi0.5Mn1.5O4 and LiCo0.5Mn1.5O4 sample shows more than 130 mAh/g between 3.5 and 5.2 V at a current density of 0.65 mA/cm2 and well developed plateau around 5 V, respectively.

The reversal of the spontaneous exchange bias effect and zero-field-cooling magnetization in La1.5Sr0.5Co1-xFexMnO6: the effect of Fe doping.

PubMed

Zhang, H G; Xie, L; Liu, X C; Xiong, M X; Cao, L L; Li, Y T

2017-09-20

The crystal structure, electronic structure and magnetic properties were systematically studied in a series of Fe-doped La 1.5 Sr 0.5 CoMnO 6 double perovskites. The X-ray diffraction patterns of the samples are all refined with a rhombohedral (R3[combining macron]c) structure. The parameters a and c continuously increase with increasing Fe doping concentration x. X-ray photoelectron spectroscopy (XPS) spectra of the Mn, Co, and Fe 2p core levels, consistent with the soft X-ray absorption spectroscopy (XAS) spectra of Mn, Co, and Fe L 2,3 edges, indicate that their valence states are Mn 3+ and Mn 4+ , Co 2+ and Co 3+ , and Fe 3+ , respectively. However, relative to samples with x ≤ 0.1, there is an abrupt change of photon energy in the Co- and Fe-2p XAS spectra for x ≥ 0.2, implying the spin state transition is from high to low. In addition, this is further confirmed by a comparison between the calculated effective spin moment from the paramagnetic data and the theoretical value. Interestingly, we demonstrate the reversal of both zero-field-cooling magnetization and the sign switching of the spontaneous exchange bias (SEB) with the doping concentration from magnetic measurements. The magnetization reverses from positive to negative with the temperature decreasing across the compensation temperature at the critical concentration x = 0.2. Meanwhile, the exchange bias field of the SEB reverses from large negative values to positive ones. Our findings allow us to propose that the spin state transition caused by inhomogeneity is considered to play an important role in the reversal of the magnetization and the SEB effect.

Optical spectra of the colloidal Fe-doped manganate CaMn1- x Fe x O3 ( x = 0, 0.01, 0.03, 0.05)

NASA Astrophysics Data System (ADS)

Pham, Duc Huyen Yen; Nguyen, Duc Tho; Pham, Duc Thang; Hoang, Nam Nhat; Pham, The Tan

2013-06-01

We report the optical behaviors of the Fe-doped CaMnO3 family of compounds at low doping concentrations x ≤ 5%. The study aims at assisting the evaluation of the competition between ferroand antiferromagnetic orderings, which is believed to be a cause of many interesting properties of this class of compounds, including the magnetization reversal effect recently discovered. The structural characterization showed a predominant orthorhombic phase with slightly increased cell constants due to doping. The Raman spectra revealed changes associated with the Mn sites, and the IR absorption spectrum showed a characteristic Fe band at 1.2 eV, which should be accompanied by a change of spin. The analysis of the magnetization data allowed us to predict that while the doping reduced the ferromagnetic coupling strength, and therefore the T C , the maximal doping concentration for the effective exchange to be zero was around 14%.

Effect of Sm substitution on magnetic and magnetocaloric properties of La0.7-xSmxBa0.3MnO3 (0 ≤ x ≤ 0.2) compounds

NASA Astrophysics Data System (ADS)

Modi, Anchit; Gaur, N. K.

2017-11-01

In the present paper we have studied the effect of Sm doping on the magnetic and magnetocaloric properties of La0.7-xSmxBa0.3MnO3 (0 ≤ x ≤ 0.2) compounds. These sample have been synthesized by conventional solid state reaction method. The analysis of synthesized samples by X-ray diffraction showed that the formation of single phase compositions and doping of La3+ by Sm3+ ion converted the chemical structure form rhombohedral (R-3C) to orthorhombic (Imma). The magnetic study measurement specified that the ferromagnetic double exchange interaction is weakened with increasing Sm content as a consequence of the curie temperature (Tc) shift in lower temperature from 340 K for x = 0, 290 K for x = 0.1 and 225 K for x = 0.2 compounds. Using the Banerjee's criterion plots, it is found that the phase transition for all samples in the second-order. All reported compounds exhibit a maximum and large magneto-caloric effect near the Curie temperature (Tc). The magnitude of the maximum magnetic entropy change is found to be decrease with increasing of Sm doping content i.e. 4.39 J/kg K for x = 0, 4.22 J/kg K for x = 0.1 and 2.48 J/kg K for x = 0.2 in applied field change of 5T. The trend of large entropy change and the convenient adjustment of the Curie temperature make these oxides useful for magnetic refrigeration in an extended high and low temperature even at near room temperature.

Temperature Dependence Discontinuity in the Stability of Manganese doped Ceria Nanocrystals

DOE PAGES

Wu, Longjia; Dholabhai, Pratik; Uberuaga, Blas P.; ...

2017-01-05

CeO 2 has strong potential for chemical-looping water splitting. It has been shown that manganese doping decreases interface energies of CeO 2, allowing increased stability of high surface areas in this oxygen carrier oxide. The phenomenon is related to the segregation of Mn3+ at interfaces, which causes a measurable decrease in excess energy. Here in the present work, it is shown that, despite the stability of nanocrystals of manganese-doped CeO 2 with relation to undoped CeO 2, the effect is strongly dependent on the oxidation state of manganese, i.e., on the temperature. At temperatures below 800 °C, Mn is inmore » the 3+ valence state, and coarsening is hindered by the reduced interface energetics, showing smaller crystal sizes with increasing Mn content. At temperatures above 800 °C, Mn is reduced to its 2+ valence state, and coarsening is enhanced with increasing Mn content. Atomistic simulations show the segregation of Mn to grain boundaries is relatively insensitive to the charge state of the dopant. However, point defect modeling finds that the reduced state causes a decrease in cation vacancy concentration and an increase in cation interstitials, reducing drag forces for grain boundary mobility and increasing growth rates.« less

Electronic structure study of wide band gap magnetic semiconductor (La0.6Pr0.4)0.65Ca0.35MnO3 nanocrystals in paramagnetic and ferromagnetic phases

NASA Astrophysics Data System (ADS)

Dwivedi, G. D.; Joshi, Amish G.; Kumar, Shiv; Chou, H.; Yang, K. S.; Jhong, D. J.; Chan, W. L.; Ghosh, A. K.; Chatterjee, Sandip

2016-04-01

X-ray circular magnetic dichroism (XMCD), X-ray photoemission spectroscopy (XPS), and ultraviolet photoemission spectroscopy (UPS) techniques were used to study the electronic structure of nanocrystalline (La0.6Pr0.4)0.65Ca0.35MnO3 near Fermi-level. XMCD results indicate that Mn3+ and Mn4+ spins are aligned parallel to each other at 20 K. The low M-H hysteresis curve measured at 5 K confirms ferromagnetic ordering in the (La0.6Pr0.4)0.65Ca0.35MnO3 system. The low temperature valence band XPS indicates that coupling between Mn3d and O2p is enhanced and the electronic states near Fermi-level have been suppressed below TC. The valence band UPS also confirms the suppression of electronic states near Fermi-level below Curie temperature. UPS near Fermi-edge shows that the electronic states are almost absent below 0.5 eV (at 300 K) and 1 eV (at 115 K). This absence clearly demonstrates the existence of a wide band-gap in the system since, for hole-doped semiconductors, the Fermi-level resides just above the valence band maximum.

Color stable manganese-doped phosphors

DOEpatents

Lyons, Robert Joseph [Burnt Hills, NY; Setlur, Anant Achyut [Niskayuna, NY; Deshpande, Anirudha Rajendra [Twinsburg, OH; Grigorov, Ljudmil Slavchev [Sofia, BG

2012-08-28

A process for preparing color stable Mn.sup.+4 doped phosphors includes providing a phosphor of formula I; A.sub.x[MF.sub.y]:Mn.sup.+4 I and contacting the phosphor in particulate form with a saturated solution of a composition of formula II in aqueous hydrofluoric acid; A.sub.x[MF.sub.y]; II wherein A is Li, Na, K, Rb, Cs, NR.sub.4 or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; R is H, lower alkyl, or a combination thereof; x is the absolute value of the charge of the [MF.sub.y] ion; and y is 5, 6 or 7. In particular embodiments, M is Si, Ge, Sn, Ti, Zr, or a combination thereof. A lighting apparatus capable of emitting white light includes a semiconductor light source; and a phosphor composition radiationally coupled to the light source, and which includes a color stable Mn.sup.+4 doped phosphor.

Dielectric properties of doping-free NaMn{sub 7}O{sub 12}: Origin of the observed colossal dielectric constant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cabassi, R.; Bolzoni, F.; Gauzzi, A.

2006-07-15

The semiconducting NaMn{sub 7}O{sub 12} is a doping-free compound with several coexistent properties such as orbital ordering, charge ordering, and magnetic orderings of different types. We investigated its dielectric response by means of frequency impedance measurements in the range from 20 Hz to 1 MHz. Standard measurements on metallized samples exhibit an apparent colossal dielectric constant (CDC) with an {epsilon}{sub R} value of several thousands at low frequencies, but a careful equivalent circuit analysis allows one to ascribe the observed CDC to the effect of a depletion layer on the metal-semiconductor junctions. We bypass this effect by means of amore » nonstandard technique employing mica linings: the resulting dielectric behavior exhibits the presence of the charge ordering transition at T{sub CO}=176 K and shows a net bulk dielectric constant value {epsilon}{sub R}{approx_equal}68 at room temperature.« less

Structure and electrical properties of Cu-doped Mn-Co-O spinel prepared via soft chemistry and its application in intermediate-temperature solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Brylewski, T.; Kruk, A.; Bobruk, M.; Adamczyk, A.; Partyka, J.; Rutkowski, P.

2016-11-01

The study describes CuxMn1.25-0.5xCo1.75-0.5xO4 (x = 0, 0.1, 0.3 and 0.5) spinels synthesized using EDTA gel processes in order to optimize the performance of high-quality spinel protective-conducting films deposited on steel interconnects. The powders obtained after 12 h of calcination in air at 1073 K are solely cubic spinels. Sintering these spinels for 12 h in air at 1423 K also leads to the formation of small amounts of CoO, Mn2O3 or CuO; the type of phase depends on the quantity of copper introduced into the manganese-cobalt lattice. The highest electrical conductivity at 1073 K is observed for Cu0.3Mn1.1Co1.6O4 (162 S·cm-1), which is closely correlated with the lowest activation energy of conduction over the entire temperature range (373≤T≤1073 K); the lowest conductivity is measured for Mn1.25Co1.75O4 (84 Sṡcm-1). The study confirms the suitability of the Cu0.3Mn1.1Co1.6O4 spinel as a potential material for the preparation of protective-conducting coatings on the surface of the DIN 50049 ferritic steel applied in IT-SOFC interconnects. The area-specific resistance of coated steel is 0.08 Ω·cm2, which is lower than that of bare steel after 300 h of oxidation at 1073 K. Cr vaporization tests show that the Cu0.3Mn1.1Co1.6O4 coating is efficient at blocking the outward diffusion of chromium.

Cu2+ Dual-Doped Layer-Tunnel Hybrid Na0.6Mn1- xCu xO2 as a Cathode of Sodium-Ion Battery with Enhanced Structure Stability, Electrochemical Property, and Air Stability.

PubMed

Chen, Ting-Ru; Sheng, Tian; Wu, Zhen-Guo; Li, Jun-Tao; Wang, En-Hui; Wu, Chun-Jin; Li, Hong-Tai; Guo, Xiao-Dong; Zhong, Ben-He; Huang, Ling; Sun, Shi-Gang

2018-03-28

Sodium-ion batteries (SIBs) have been regarded as a promising candidate for large-scale renewable energy storage system. Layered manganese oxide cathode possesses the advantages of high energy density, low cost and natural abundance while suffering from limited cycling life and poor rate capacity. To overcome these weaknesses, layer-tunnel hybrid material was developed and served as the cathode of SIB, which integrated high capacity, superior cycle ability, and rate performance. In the current work, the doping of copper was adopted to suppress the Jahn-Teller effect of Mn 3+ and to affect relevant structural parameters. Multifunctions of the Cu 2+ doping were carefully investigated. It was found that the structure component ratio is varied with the Cu 2+ doping amount. Results demonstrated that Na + /vacancy rearrangement and phase transitions were suppressed during cycling without sacrificing the reversible capacity and enhanced electrochemical performances evidenced with 96 mA h g -1 retained after 250 cycles at 4 C and 85 mA h g -1 at 8 C. Furthermore, ex situ X-ray diffraction has demonstrated high reversibility of the Na 0.6 Mn 0.9 Cu 0.1 O 2 cathode during Na + extraction/insertion processes and superior air stability that results in better storage properties. This study reveals that the Cu 2+ doping could be an effective strategy to tune the properties and related performances of Mn-based layer-tunnel hybrid cathode.

Reentrant metal-insulator transition in the Cu-doped manganites La1-x Pbx MnO3 (x˜0.14) single crystals

NASA Astrophysics Data System (ADS)

Zhao, B. C.; Song, W. H.; Ma, Y. Q.; Ang, R.; Zhang, S. B.; Sun, Y. P.

2005-10-01

Single crystals of La1-x Pbx Mn1-y-z Cuy O3 ( x˜0.14 ; y=0 ,0.01,0.02,0.04,0.06; z=0.02 ,0.08,0.11,0.17,0.20) are grown by the flux growth technique. The effect of Cu doping at the Mn-site on magnetic and transport properties is studied. All studied samples undergo a paramagnetic-ferromagnetic transition. The Curie temperature TC decreases and the transition becomes broader with increasing Cu-doping level. The high-temperature insulator-metal (I-M) transition moves to lower temperature with increasing Cu-doping level. A reentrant M-I transition at the low temperature T* is observed for samples with y⩾0.02 . In addition, T* increases with increasing Cu-doping level and is not affected by applied magnetic fields. Accompanying the appearance of T* , there exists a large, almost constant magnetoresistance (MR) below T* except for a large MR peak near TC . This reentrant M-I transition is ascribed to charge carrier localization due to lattice distortion caused by the Cu doping at Mn sites.

Magnetism in Complex Oxide Heterostructures Determined with Neutron Scattering

NASA Astrophysics Data System (ADS)

Te Velthuis, Suzanne G. E.

2009-03-01

With the creation of high quality superlattices consisting of complex oxide materials novel materials exhibiting a wide range of interesting phenomena are emerging. Due to the diverse physical properties of complex oxides, (e.g., ferromagnetism, antiferromagnetism, superconductivity), some of which can be varied by doping, the versatility in their applications is large. The physical properties in these new materials, often is tied to the behavior at the interfaces between the different components of the superlattice, and therefore requires detailed knowledge of the relationship between the chemical and electronic composition. Polarized neutron reflectometry (PNR) provides access to the depth-dependent magnitude and orientation of the magnetization and can therefore link the magnetic to the electronic and chemical properties, especially close to these interfaces. Several examples of our work will be presented, including that on La0.7Ca0.3MnO3/ YBa2Cu3O7-δ/ La0.7Ca0.3MnO3 trilayers which exhibit the inverse superconducting spin switch behavior, and where suppression of the magnetization close to the interface, as well as a varying anisotropy axis have been determined [1]. Another example is work on digitally layered analogs of La1-xSrxMnO3, where PNR reveals an asymmetric distribution of the magnetization across the two components (antiferromagnetic) LaMnO3and SrMnO3, which has been linked to structural properties at the interfaces [2]. [4pt] [1] V. Peña, Z. Sefrioui, D. Arias, C. Leon, J. Santamaria, J. L. Martinez, S. G. E. te Velthuis, A. Hoffmann, Phys. Rev. Lett. 94 (2005) 057002. [0pt] [2] S. J. May, A. B. Shah, S. G. E. te Velthuis, M. R. Fitzsimmons, J. M. Zuo, X. Zhai, J. N. Eckstein, S. D. Bader, and A. Bhattacharya, Phys. Rev. B 77 (2008) 174409.

The magnetic ordering in high magnetoresistance Mn-doped ZnO thin films

DOE PAGES

Venkatesh, S.; Baras, A.; Lee, J. -S.; ...

2016-03-24

Here, we studied the nature of magnetic ordering in Mn-doped ZnO thin films that exhibited ferromagnetism at 300 K and superparamagnetism at 5 K. We directly inter-related the magnetisation and magnetoresistance by invoking the polaronpercolation theory and variable range of hopping conduction below the metal-to-insulator transition. By obtaining a qualitative agreement between these two models, we attribute the ferromagnetism to the s-d exchange-induced spin splitting that was indicated by large positive magnetoresistance (~40 %). Low temperature superparamagnetism was attributed to the localization of carriers and non-interacting polaron clusters. This analysis can assist in understanding the presence or absence of ferromagnetismmore » in doped/un-doped ZnO.« less

Synthesis and characterization of three-dimensional transition metal ions doped zinc oxide based dilute magnetic semiconductor thin films

NASA Astrophysics Data System (ADS)

Samanta, Kousik

Dilute magnetic semiconductors (DMS), especially 3d-transition metal (TM) doped ZnO based DMS materials are the most promising candidates for optoelectronics and spintronics applications; e.g. in spin light emitting diode (SLED), spin transistors, and spin field effect transistors (SFET), etc. In the present dissertation, thin films of Zn1-xTMxO (TM = Co2+, Cu2+, and Mn2+) were grown on (0001) oriented Al2O3 substrates by pulsed laser deposition (PLD) technique. The films were highly c-axis oriented, nearly single crystalline, and defects free for a limited concentration of the dilution of transition metal ions. In particular, we have obtained single crystalline phases of Zn1-xTMxO thin films for up to 10, 3, and 5 stoichiometric percentages of Co2+, Cu2+, and Mn2+ respectively. Raman micro-probe system was used to understand the structural and lattice dynamical properties at different physical conditions. The confinement of optical phonons in the disorder lattice was explained by alloy potential fluctuation (APF) using a spatial correlation (SC) model. The detailed analysis of the optical phonon behavior in disorder lattice confirmed the substitution of the transition metal ions in Zn 2+ site of the ZnO host lattice. The secondary phases of ZnCo 2O4, CuO, and ZnMn2O4 were detected in higher Co, Cu, and Mn doped ZnO thin films respectively; where as, XRD did not detect these secondary phases in the same samples. Room temperature ferromagnetism was observed in Co2+ and Cu2+ ions doped ZnO thin films with maximum saturation magnetization (Ms) of 1.0 and 0.76 muB respectively. The origin of the observed ferromagnetism in Zn1-xCoxO thin films was tested by the controlled introduction of shallow donors (Al) in Zn0.9-x Co0.1O:Alx (x = 0.005 and 0.01) thin films. The saturation magnetization for the 10% Co-doped ZnO (1.0 muB /Co) at 300K reduced (˜0.25 muB/Co) due to Al doping. The observed ferromagnetism and the reduction due to Al doping can be explained by the Bound Magnetic Polaron (BMP) model. The Resistivity of ZCO sample (˜ 103 O-cm) dropped by 5 orders of magnitude (0.02 O-cm) in Co, Al co-doped samples and the carrier concentrations increases 4 orders of magnitude (˜ 1019/cm3). The Cu2+ doped ZnO thin films showed the ferromagnetic property at 300K. The p-d orbital mixing of high spin Cu2+ (d9) state with the nearest neighbor oxygen p-orbital can explain the origin of RTFM in Zn 1-xCuxO thin films. The optical transmission spectroscopy and the photoluminescence spectroscopy analysis were used to understand the electronic band structure, near band edge (NBE) transition, and the excitonic behavior in ZnO and Zn1-xTMxO thin films. We have found the reduction of NBE transition at 300K due to the substitution of Co and Cu in ZnO host lattice. This narrowing of the optical band gap (NBE) is due to the sp-d exchange interaction between the d electrons of transition metal ions and the band electrons of ZnO; the strength of this interaction strongly depends on the number of d electrons. The s-d and p-d exchanges give rise to negative and positive corrections to the conduction and valance band edges respectively, leading to the NBE narrowing. We have observed the characteristic inter atomic d-d transitions in Co doped samples; thus confirming the substitution of Co2+ in the tetrahedral site in ZnO. The low temperature (77K) PL spectrum showed the basic excitonic characteristics of pure ZnO in Zn1-xTMxO thin films. The X-ray photoelectron spectroscopy (XPS) showed that the Co and Cu are normally in 2+ oxidation state, but in the case of higher Cu concentrations (>3%), the mixed state of Cu2+ and Cu1+ were detected.

Spectroscopic properties of (PVA+ZnO):Mn{sup 2+} polymer films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rani, Ch.; Raju, D. Siva; Bindu, S. Hima

2015-05-15

Electron Paramagnetic Resonance (EPR), optical absorption and infrared spectral studies have been carried out on Mn{sup 2+} ions doped in poly(vinyl alcohol) complexed with zinc oxide polymer films prepared by solution cast technique. The EPR spectra of 1 mol% Mn{sup 2+} ions doped polymer complex (PVA+ZnO) at room temperature exhibit sextet hyperfine structure (hfs), centered at 2.01. The spin-Hamiltonian parameter values indicate that the ground state of Mn{sup 2+} ion in d{sup 5} and the site symmetry around Mn{sup 2+} ions in tetragonally distorted octa hedral site. The optical absorption spectra exhibits two bands centered at 275nm at 437nm. Themore » FTIR spectrum exhibits bands characteristic of stretching and banding vibrations of O-H, C-H and C=C groups.« less

DENSITY FUNCTIONAL STUDY OF ELEMENTAL MERCURY ADSORPTION ON X (X=Mn, Si, Ti, Al, AND Zn)-DOPED CuO (110) SURFACE

NASA Astrophysics Data System (ADS)

He, Ping; Peng, Xiaolong; Zhang, Zhongzhi; Wu, Jiang; Chen, Naichao; Ren, Jianxing

Copper oxide (CuO) is proved to be a potential adsorbent for elemental mercury in the flue gas emitted from coal-fired power plant. However, the O-terminated CuO(110) surface has relatively week adsorption capacity for Hg. In this work, the doped method is applied to enhance the mercury adsorption capacity of O-terminated CuO(110). Mn, Si, Ti, Al and Zn are selected as the doped atom. It is found that only Zn-doped CuO (110) surfaces have the higher adsorption energy than the pure O-terminated CuO(110) surface. The mercury adsorption capacity is a complex issue, which depends on a combination of oxygen and doped element. The results suggest that the lower electropositive doped element is favorable for the improvement of mercury adsorption capacity. However, the lower electronegativity of oxygen atoms does not facilitate the mercury capture, which is different from the organic material. Cu and doped metal element, rather than oxygen atom, mainly determine mercury adsorption capacity of O-terminated CuO(110) surface, which leads to the lower adsorption capacity of the O-terminated CuO(110) surface than the Cu-terminated CuO(110) surface. The conclusions can also offer a valuable reference for the other metal oxide regarding mercury capture.

High-performance of bare and Ti-doped α-MnO2 nanoparticles in catalyzing the Oxygen Reduction Reaction

NASA Astrophysics Data System (ADS)

Pargoletti, E.; Cappelletti, G.; Minguzzi, A.; Rondinini, S.; Leoni, M.; Marelli, M.; Vertova, A.

2016-09-01

Nanostructured MnO2 has unique electrocatalytic properties towards the Oxygen Reduction Reaction (ORR, the main cathodic reaction in metal-air devices), representing an excellent alternative to the expensive platinum. Herein, we report the hydrothermal synthesis of bare and 5% Ti-doped α-MnO2 nanoparticles using two different oxidizing agents, namely ammonium persulfate for MH_N samples and potassium permanganate for MH_K ones. The physico-chemical characterizations show that oxidant cations induce different structural, morphological and surface properties of the final powders. Hence, correlations between the different α-MnO2 characteristics and their electrocatalytic performances towards the ORR are drawn, highlighting the diverse effect even on the kinetic point of view. The ORR activity in alkaline media is examined by means of Staircase - Linear Sweep Voltammetry (S-LSV), using Gas Diffusion Electrode (GDE) as the air-cathode. The presence of these nanoparticles in the GDEs leads to a significant shift of the ORR onset potential (∼100 mV) towards less cathodic values, underlining the electrocatalytic efficiency of all the nanopowders. Furthermore, high exchange current densities (j0) are determined for GDEs with Ti-doped MnO2, comparable to the well-performing Pd45Pt5Sn50, and making it a promising material for the ORR.

Structural, transport and magnetotransport properties of Ru-doped La0.5Sr0.5Mn1-xRuxO3 (x = 0.0 & 0.05) manganite

NASA Astrophysics Data System (ADS)

Jethva, Sadaf; Katba, Savan; Udeshi, Malay; Kuberkar, D. G.

2017-09-01

We report the results of the structural, transport and magnetotransport studies on polycrystalline La0.5Sr0.5Mn1-xRuxO3 (x = 0.0 and 0.05) manganite investigated using XRD and resistivity (with and without field) measurements. Rietveld refinement of XRD patterns confirms the single phasic tetragonal structure for both the samples crystalizing in I4/mcm space group (No. 140). Low-temperature resistivity and MR measurements with H = 0 T & 5 T field show thermal hysteresis which has been attributed to the first order phase transition. The increase in resistivity and decrease in metal - insulator transition temperature (TMI) with Ru - doping concentration in La0.5Sr0.5MnO3 (LSMO) has been understood in the context of superexchange interaction between Mn and Ru ions. The observed upturn in resistivity at low temperature under field has been explained using combined effect of electron - electron (e - e) interaction, Kondo-like spin-dependent scattering and electron - phonon interaction while the variation in resistivity at high temperature (T > Tp) has been explained using adiabatic small polaron hopping model.

Screen-printed calcium-birnessite electrodes for water oxidation at neutral pH and an "electrochemical harriman series".

PubMed

Lee, Seung Y; González-Flores, Diego; Ohms, Jonas; Trost, Tim; Dau, Holger; Zaharieva, Ivelina; Kurz, Philipp

2014-12-01

A mild screen-printing method was developed to coat conductive oxide surfaces (here: fluorine-doped tin oxide) with micrometer-thick layers of presynthesized calcium manganese oxide (Ca-birnessite) particles. After optimization steps concerning the printing process and layer thickness, electrodes were obtained that could be used as corrosion-stable water-oxidizing anodes at pH 7 to yield current densities of 1 mA cm(-2) at an overpotential of less than 500 mV. Analyses of the electrode coatings of optimal thickness (≈10 μm) indicated that composition, oxide phase, and morphology of the synthetic Ca-birnessite particles were hardly affected by the screen-printing procedure. However, a more detailed analysis by X-ray absorption spectroscopy revealed small modifications of both the Mn redox state and the structure at the atomic level, which could affect functional properties such as proton conductivity. Furthermore, the versatile new screen-printing method was used for a comparative study of various transition-metal oxides concerning electrochemical water oxidation under "artificial leaf conditions" (neutral pH, fairly low overpotential and current density), for which a general activity ranking of RuO2 >Co3 O4 ≈(Ca)MnOx ≈NiO was observed. Within the group of screened manganese oxides, Ca-birnessite performed better than "Mn-only materials" such as Mn2 O3 and MnO2 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermoelectric Properties of Electron-Doped SrMnO3 Single Crystals with Perovskite Structure

NASA Astrophysics Data System (ADS)

Suzuki, T.; Sakai, H.; Taguchi, Y.; Tokura, Y.

2012-06-01

Thermoelectric properties have been investigated for single crystals of Sr(Mn1- x Mo x )O3 with the perovskite structure. Similar to (Sr1- x Ce x )MnO3, the Seebeck coefficient for lightly electron-doped compounds ( x ≤ 0.01) is enhanced upon G-type antiferromagnetic ordering, while maintaining metallic conduction. This results in enhancement of the figure of merit ( ZT). On the other hand, the Seebeck coefficient for the more electron-doped compound ( x = 0.025) changes sign from negative to positive within a spin and orbital ordered phase (with C-type antiferromagnetic configuration and Mn 3 z 2 - r 2 type orbital order) as the temperature is lowered, whereas the Hall coefficient remains negative in the whole temperature range. The enhancement of the ZT value in the G-type antiferromagnetic phase implies the possibility for improvement of the thermoelectric efficiency by using the coupling between charge, spin, orbital, and lattice degrees of freedom in strongly correlated electron systems.

Synthesis, structural properties and thermal stability of Mn-doped hydroxyapatite

NASA Astrophysics Data System (ADS)

Paluszkiewicz, Czesława; Ślósarczyk, Anna; Pijocha, Dawid; Sitarz, Maciej; Bućko, Mirosław; Zima, Aneta; Chróścicka, Anna; Lewandowska-Szumieł, Małgorzata

2010-07-01

Hydroxyapatite (HA) - Ca 10(PO 4) 6(OH) 2 is a basic inorganic model component of hard biological tissues, such as bones and teeth. The significant property of HA is its ability to exchange Ca 2+ ions, which influences crystallinity, physico-chemical and biological properties of modified hydroxyapatite materials. In this work, FTIR, Raman spectroscopy, XRD, SEM and EDS techniques were used to determine thermal stability, chemical and phase composition of Mn containing hydroxyapatite (MnHA). Described methods confirmed thermal decomposition and phase transformation of MnHA to αTCP, βTCP and formation of Mn 3O 4 depending on sintering temperature and manganese content. In vitro biological evaluation of Mn-modified HA ceramics was also performed using human osteoblast cells.

Corrosion behavior of pristine and added MgB2 in Phosphate Buffered Saline Solution

NASA Astrophysics Data System (ADS)

Batalu, D.; Bojin, D.; Ghiban, B.; Aldica, G.; Badica, P.

2012-09-01

We have obtained by Spark Plasma Sintering (SPS), dense samples of MgB2 added with Ho2O3. Starting composition was (MgB2)0.975(HoO1.5)0.025 and we used addition powders with an average particle size below and above 100 nm. For Mg, pristine and added MgB2 samples we measured potentiodynamic polarization curves in Phosphate Buffered Saline (PBS) solution media at room temperature. MgB2 based composites show corrosion/ degradation effects. This behavior is in principle similar to Mg based alloys in the same media. Our work suggests that the different morphologies and phase compositions of the SPS-ed samples influence the interaction with corrosion medium; hence additions can play an important role in controlling the corrosion rate. Pristine MgB2 show a significant improvement of the corrosion resistance, if compared with Mg. The best corrosion resistance is obtained for pristine MgB2, followed by MgB2 with nano-Ho2O3 and μ-Ho2O3 additions.

Thermally stimulated luminescence studies of undoped, Cu- and Mn-doped CaSO4 compounds

NASA Astrophysics Data System (ADS)

Manam, J.; Das, S.

Thermally stimulated luminescence (TSL) of undoped and doped CaSO4 with activators such as Cu and Mn has been investigated. The polycrystalline samples of undoped and doped CaSO4 are prepared by the melting method. The formation of CaSO4 compound is confirmed by X-ray diffraction and Fourier transform infrared studies. Scanning electron microscopic studies of CaSO4 are also carried out. The TSL glow curves of undoped CaSO4, Cu- and Mn-doped CaSO4 are studied. Comparison of the thermoluminescence (TL) intensity of the most intensive glow peak of Cu-doped CaSO4 compound with that of undoped CaSO4 shows that addition of Cu impurity in CaSO4 compound enhances the TL intensity by about four times. However, the addition of Mn impurity to undoped CaSO4 increases the TL intensity by about three times when compared with that of undoped CaSO4. The TL-dose dependence of all three samples was studied and was observed to be almost linear in the studied range of irradiation time. Among the samples studied, namely undoped CaSO4 and Cu- and Mn-doped CaSO4, Cu-doped CaSO4 is found to be the most sensitive. The trap parameters, namely order of kinetics (b), activation energy (E) and frequency factor (s) associated with the most intensive glow peaks of CaSO4:Mn, CaSO4:Cu and CaSO4 phosphors were determined using the glow curve shape (Chen's) method.

Polar-antipolar transition and weak ferromagnetism in Mn-doped Bi0.86La0.14FeO3

NASA Astrophysics Data System (ADS)

Khomchenko, V. A.; Karpinsky, D. V.; Troyanchuk, I. O.; Sikolenko, V. V.; Többens, D. M.; Ivanov, M. S.; Silibin, M. V.; Rai, R.; Paixão, J. A.

2018-04-01

Having been considered as a prime example of a room-temperature magnetoelectric multiferroic, BiFeO3 continues to attract much interest. Since functional properties of this material can be effectively influenced by chemical, electrical, magnetic, mechanical and thermal stimuli, it can serve as a model for the investigation of cross-coupling phenomena in solids. Special attention is currently paid to the study of chemical pressure-driven magneto-structural transformations. In this paper, we report on the effect of the Mn doping on the crystal structure and magnetic behavior of the Bi1‑x La x FeO3 multiferroics near their polar-antipolar (antiferromagnetic-weak ferromagnetic) phase boundary. Synchrotron x-ray and neutron powder diffraction measurements of the Bi0.86La0.14Fe1‑x Mn x O3 (x  =  0.05, 0.1, 0.15) compounds have been performed. The diffraction data suggest that the Mn substitution results in the suppression of the ferroelectric polarization and gives rise to the appearance of the antiferroelectric (generally, PbZrO3-related) phase characteristic of the phase diagrams of the Bi1‑x RE x FeO3 (RE  =  rare-earth) systems. Depending on the Mn concentration (determining phase composition of the Bi0.86La0.14Fe1‑x Mn x O3 samples at room temperature), either complete or partial revival of the polar phase can be observed with increasing temperature. Magnetic measurements of the samples indicate that the Mn doping affects the stability of the cycloidal antiferromagnetic order specific to the polar phase, thus resulting in the formation of a ferroelectric and weak ferromagnetic state.

First-principles theory of doping in layered oxide electrode materials

NASA Astrophysics Data System (ADS)

Hoang, Khang

2017-12-01

Doping lithium-ion battery electrode materials Li M O2 (M = Co, Ni, Mn) with impurities has been shown to be an effective way to optimize their electrochemical properties. Here, we report a detailed first-principles study of layered oxides LiCoO2, LiNiO2, and LiMnO2 lightly doped with transition-metal (Fe, Co, Ni, Mn) and non-transition-metal (Mg, Al) impurities using hybrid-density-functional defect calculations. We find that the lattice site preference is dependent on both the dopant's charge and spin states, which are coupled strongly to the local lattice environment and can be affected by the presence of codopant(s), and the relative abundance of the host compound's constituting elements in the synthesis environment. On the basis of the structure and energetics of the impurities and their complexes with intrinsic point defects, we determine all possible low-energy impurity-related defect complexes, thus providing defect models for further analyses of the materials. From a materials modeling perspective, these lightly doped compounds also serve as model systems for understanding the more complex, mixed-metal, Li M O2 -based battery cathode materials.

Impact of Microcrack Generation and Surface Degradation on a Nickel-Rich Layered Li[Ni 0.9Co 0.05Mn 0.05]O 2 Cathode for Lithium-Ion Batteries

DOE PAGES

Sun, Ho-Hyun; Manthiram, Arumugam

2017-09-13

In this work, to address the growing demand for energy density, the Ni-rich layered [Ni 0.90Co 0.05Mn 0.05]O 2 cathode has been synthesized and its electrochemical performance in lithium-ion cells has been benchmarked against a lower-Ni content Li[Ni 0.6Co 0.2Mn 0.2]O 2 cathode. Li[Ni 0.90Co 0.05Mn 0.05]O 2 delivers a high discharge capacity of 227 mA h g -1 compared to a capacity of 189 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2 when cycled up to a lower cutoff voltage of 4.3 V, making it an appealing candidate for electric vehicles. With an increase in the chargemore » cutoff voltage to 4.5 V, Li[Ni 0.90Co 0.05Mn 0.05]O 2 displays a capacity of 238 mA h g -1 compared to a capacity of 208 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2. Although Li[Ni 0.90Co 0.05Mn 0.05]O 2 suffers during cycling from the usual rapid capacity fade in a manner similar to that of LiNiO 2, 87 and 81% of the initial capacity could still be retained after 100 cycles even after cycling to higher cutoff voltages of 4.3 and 4.5 V, respectively. A comparison of Li[Ni 0.90Co 0.05Mn 0.05]O 2 and Li[Ni 0.6Co 0.2Mn 0.2]O 2 reveals that the capacity fade of Li[Ni 0.90Co 0.05Mn 0.05]O 2 originates largely from the anisotropic volume change and subsequent microcrack propagation in the bulk and NiO-like rock salt impurity phase formation on the particle surface, which are exacerbated at 4.5 V. Lastly, future work with appropriate doping and surface modification could improve further the performance of Li[Ni 0.90Co 0.05Mn 0.05]O 2.« less

Impact of Microcrack Generation and Surface Degradation on a Nickel-Rich Layered Li[Ni 0.9Co 0.05Mn 0.05]O 2 Cathode for Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Ho-Hyun; Manthiram, Arumugam

In this work, to address the growing demand for energy density, the Ni-rich layered [Ni 0.90Co 0.05Mn 0.05]O 2 cathode has been synthesized and its electrochemical performance in lithium-ion cells has been benchmarked against a lower-Ni content Li[Ni 0.6Co 0.2Mn 0.2]O 2 cathode. Li[Ni 0.90Co 0.05Mn 0.05]O 2 delivers a high discharge capacity of 227 mA h g -1 compared to a capacity of 189 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2 when cycled up to a lower cutoff voltage of 4.3 V, making it an appealing candidate for electric vehicles. With an increase in the chargemore » cutoff voltage to 4.5 V, Li[Ni 0.90Co 0.05Mn 0.05]O 2 displays a capacity of 238 mA h g -1 compared to a capacity of 208 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2. Although Li[Ni 0.90Co 0.05Mn 0.05]O 2 suffers during cycling from the usual rapid capacity fade in a manner similar to that of LiNiO 2, 87 and 81% of the initial capacity could still be retained after 100 cycles even after cycling to higher cutoff voltages of 4.3 and 4.5 V, respectively. A comparison of Li[Ni 0.90Co 0.05Mn 0.05]O 2 and Li[Ni 0.6Co 0.2Mn 0.2]O 2 reveals that the capacity fade of Li[Ni 0.90Co 0.05Mn 0.05]O 2 originates largely from the anisotropic volume change and subsequent microcrack propagation in the bulk and NiO-like rock salt impurity phase formation on the particle surface, which are exacerbated at 4.5 V. Lastly, future work with appropriate doping and surface modification could improve further the performance of Li[Ni 0.90Co 0.05Mn 0.05]O 2.« less

(Bi,Sr) (Fe1−x,Mx)O3−δ (M = Co, Ni and Mn) Cathode Materials with Mixed Electro-Ionic Conductivity

PubMed Central

Wei, Wen-Cheng J.; Huang, Der-Rong; Wang, Dan

2016-01-01

(Bi,Sr)FeO3−δ (BSF) cathode materials doped with either Co, Ni or Mn are synthesized by an ethylene diamine tetra-acetic acid (EDTA)-citrate complexing method, and the effects of the doping level on the mixed electronic-ionic conductivity at various temperatures are studied up to 800 °C. The phase purity and solid solution limit are investigated by X-ray diffraction (XRD). The ionic conductivity is measured by the four-probe direct current (DC) method, the valence state of Fe and Mn by X-ray photoelectron spectroscopy (XPS), and the oxygen non-stoichiometry by differential thermo-gravimetric analysis (TGA). The doped ferrites show interesting electronic conductivity dependent on the testing temperature, implying two conductive mechanisms, either controlled by double exchange at lower temperatures or small polaron (electron-oxygen vacancy) conduction at temperatures greater than 400 °C. The results of Co-doped BSF (S50C20) show the best mixed conductivity among the ferrites, and this is used to assemble cells. The cell with a S50C20 cathode in the region of 600–800 °C is improved by 15% in maximum power density greater than the cell with La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) due to the balanced contribution from oxygen ions, vacancies and electrons. PMID:28774043

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lingyan, E-mail: l.y.wang@mail.xjtu.edu.cn, E-mail: wren@mail.xjtu.edu.cn; Ren, Wei, E-mail: l.y.wang@mail.xjtu.edu.cn, E-mail: wren@mail.xjtu.edu.cn; Shi, Peng

Lead-free ferroelectric un-doped and doped K{sub 0.5}Na{sub 0.5}NbO{sub 3} (KNN) films with different amounts of manganese (Mn) were prepared by a chemical solution deposition method. The thicknesses of all films are about 1.6 μm. Their phase, microstructure, leakage current behavior, and electrical properties were investigated. With increasing the amounts of Mn, the crystallinity became worse. Fortunately, the electrical properties were improved due to the decreased leakage current density after Mn-doping. The study on leakage behaviors shows that the dominant conduction mechanism at low electric field in the un-doped KNN film is ohmic mode and that at high electric field is space-charge-limitedmore » and Pool-Frenkel emission. After Mn doping, the dominant conduction mechanism at high electric field of KNN films changed single space-charge-limited. However, the introduction of higher amount of Mn into the KNN film would lead to a changed conduction mechanism from space-charge-limited to ohmic mode. Consequently, there exists an optimal amount of Mn doping of 2.0 mol. %. The 2.0 mol. % Mn doped KNN film shows the lowest leakage current density and the best electrical properties. With the secondary ion mass spectroscopies and x-ray photoelectron spectroscopy analyses, the homogeneous distribution in the KNN films and entrance of Mn element in the lattice of KNN perovskite structure were also confirmed.« less

Red Emission of SrAl2O4:Mn4+ Phosphor for Warm White Light-Emitting Diodes

NASA Astrophysics Data System (ADS)

Chi, N. T. K.; Tuan, N. T.; Lien, N. T. K.; Nguyen, D. H.

2018-05-01

In this work, SrAl2O4:Mn4+ phosphor is prepared by co-precipitation. The phase structure, morphology, composition and luminescent performance of the phosphor are investigated in detail with x-ray diffraction, field emission scanning electron microscopy, steady-state photoluminescence (PL) spectra, and temperature-dependent PL measurements. The phosphor shows a strong red emission peak at ˜ 690 nm, which is due to the transition between electronic levels and the electric dipole transition 2Eg to 4A2g of Mn4+ ions located at the sites with D3d local symmetry. The sample doped with 0.04 mol.% Mn4+ exhibits intense red emission with high thermal stability and appropriate International Commission on Illumination (CIE) coordinates (x = 0.6959, y = 0.2737). It is also found that the phosphor absorption in an extended band from 250 nm to 500 nm has three peaks at 320 nm, 405 nm, and 470 nm, which match well with the emission band of ultraviolet (UV) lighting emission diode (LED) or blue LED chips. These results demonstrate that SrAl2O4:Mn4+ phosphor can play the role of activator in narrow red-emitting phosphor, which is potentially useful in UV (˜ 320 nm) or blue (˜ 460 nm) LED.

Structural and morphological studies on Bi{sub 1-x}Ca{sub x}MnO{sub 3} thin films grown by RF magnetron sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pugazhvadivu, K. S.; Santhiya, M.; Tamilarasan, K., E-mail: dr.k.tamilarasan@gmail.com

2016-05-23

Bi{sub 1-x}Ca{sub x}MnO{sub 3} (0 ≤ X ≤ 0.4) thin films are deposited on n–type Si (100) substrate at 800 °C by RF magnetron sputtering. X-ray diffraction pattern shows that the films are crystallized in monoclinic structure with C2 space group. The crystallite size and induced strain in the prepared films are measured by W-H plot. The cell parameters and texture coefficient of the films are calculated. The surface morphology of the films is examined by atomic force microscope. The study confirms the optimum level of calcium doping is 20 at. % in Bi site of BiMnO{sub 3} film, thesemore » findings pave the way for further research in the Ca modified BiMnO{sub 3} films towards device fabrication.« less

Fabrication of predominantly Mn4+ -doped TiO2 nanoparticles under equilibrium conditions and their application as visible-light photocatalyts.

PubMed

Wang, Lijie; Fan, Jiajie; Cao, Zetan; Zheng, Yichao; Yao, Zhiqiang; Shao, Guosheng; Hu, Junhua

2014-07-01

The chemical state of a transition-metal dopant in TiO(2) can intrinsically determine the performance of the doped material in applications such as photocatalysis and photovoltaics. In this study, manganese-doped TiO2 is fabricated by a near-equilibrium process, in which the TiO(2) precursor powder precipitates from a hydrothermally obtained transparent mother solution. The doping level and subsequent thermal treatment influence the morphology and crystallization of the TiO(2) samples. FTIR spectroscopy and X-ray photoelectron spectroscopy analyses indicate that the manganese dopant is substitutionally incorporated by replacing Ti(4+) cations. The absorption band edge can be gradually shifted to 1.8 eV by increasing the nominal manganese content to 10 at %. Manganese atoms doped into the titanium lattice are associated with the dominant 4+ valence oxidation state, which introduces two curved, intermediate bands within the band gap and results in a significant enhancement in photoabsorption and the quantity of photogenerated hydroxyl radicals. Additionally, the high photocatalytic performance of manganese-doped TiO(2) is also attributed to the low oxygen content, owing to the equilibrium fabrication conditions. This work provides an important strategy to control the chemical and defect states of dopants by using an equilibrium fabrication process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

DOE PAGES

Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia; ...

2017-10-31

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substratemore » with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substratemore » with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

Interlinked multiphase Fe-doped MnO2 nanostructures: a novel design for enhanced pseudocapacitive performance.

PubMed

Wang, Ziya; Wang, Fengping; Li, Yan; Hu, Jianlin; Lu, Yanzhen; Xu, Mei

2016-04-07

Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g(-1) even under a high mass loading (∼5 mg cm(-2)). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm(-3)) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g(-1). The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices.

Co3O4/MnO2/Hierarchically Porous Carbon as Superior Bifunctional Electrodes for Liquid and All-Solid-State Rechargeable Zinc-Air Batteries.

PubMed

Li, Xuemei; Dong, Fang; Xu, Nengneng; Zhang, Tao; Li, Kaixi; Qiao, Jinli

2018-05-09

The design of efficient, durable, and affordable catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is very indispensable in liquid-type and flexible all-solid-state zinc-air batteries. Herein, we present a high-performance bifunctional catalyst with cobalt and manganese oxides supported on porous carbon (Co 3 O 4 /MnO 2 /PQ-7). The optimized Co 3 O 4 /MnO 2 /PQ-7 exhibited a comparable ORR performance with commercial Pt/C and a more superior OER performance than all of the other prepared catalysts, including commercial Pt/C. When applied to practical aqueous (6.0 M KOH) zinc-air batteries, the Co 3 O 4 /MnO 2 /porous carbon hybrid catalysts exhibited exceptional performance, such as a maximum discharge peak power density as high as 257 mW cm -2 and the most stable charge-discharge durability over 50 h with negligible deactivation to date. More importantly, a series of flexible all-solid-state zinc-air batteries can be fabricated by the Co 3 O 4 /MnO 2 /porous carbon with a layer-by-layer method. The optimal catalyst (Co 3 O 4 /MnO 2 /PQ-7) exhibited an excellent peak power density of 45 mW cm -2 . The discharge potentials almost remained unchanged for 6 h at 5 mA cm -2 and possessed a long cycle life (2.5 h@5 mA cm -2 ). These results make the optimized Co 3 O 4 /MnO 2 /PQ-7 a promising cathode candidate for both liquid-type and flexible all-solid-state zinc-air batteries.

Rare earth doped zinc oxide varistors

DOEpatents

McMillan, A.D.; Modine, F.A.; Lauf, R.J.; Alim, M.A.; Mahan, G.D.; Bartkowiak, M.

1998-12-29

A varistor includes a Bi-free, essentially homogeneous sintered body of a ceramic composition including, expressed as nominal weight %, 0.2--4.0% oxide of at least one rare earth element, 0.5--4.0% Co{sub 3}O{sub 4}, 0.05--0.4% K{sub 2}O, 0.05--0.2% Cr{sub 2}O{sub 3}, 0--0.2% CaO, 0.00005--0.01% Al{sub 2}O{sub 3}, 0--2% MnO, 0--0.05% MgO, 0--0.5% TiO{sub 3}, 0--0.2% SnO{sub 2}, 0--0.02% B{sub 2}O{sub 3}, balance ZnO. 4 figs.

Investigation of structural and electrical properties of La{sub 0.7}(Ba{sub 1-x}Ca{sub x}){sub 0.3}MnO{sub 3} compounds by sol-gel method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winarsih, Suci; Kurniawan, Budhy, E-mail: bkuru07@gmail.com; Manaf, Azwar

2016-06-17

In this paper, we explored structural and electrical properties of La{sub 0.7}(Ba{sub 1-x}Ca{sub x}){sub 0.3}MnO{sub 3} (x = 0; 0.03; and 0.05) compounds. The general structure of perovskite manganites is AMnO{sub 3} (A= trivalent rare earth with divalent ion-doped). Average A-site cation size, external pressure, and the variance of the cation size σ{sup 2} are one of many factors that affected to magneto-transport properties of manganites as reported by others. In this work we focus only on the electrical properties in La{sub 0.7}Ba{sub 0.3}MnO{sub 3} Ca-doped compound which may influence crystal structure resulting resistivity phenomena under magnetic field influence. Allmore » samples were synthesized by sol-gel method from which fine powders were obtained. The X-ray powder diffraction pattern of powder materials shows that all samples are fully crystalline with a rhombohedral structure. Rietveld refinement shows that the presence of calcium has changed some crystal structural parameters such lattice parameter, Mn–O bond length, and Mn–O–Mn angles. The electrical resistivity of all synthesized materials investigated by four point probe method using Cryogenic Magnet in the temperature range of 50-300 K under influence a magnetic field shows resistivity temperature dependent. In fact presence of calcium has reduced the resistivity. It might occure because it has made an enhancement in the mobility of hopping electrons. The magnetic external field causes the resistivity decreased for all samples because host spin align by delocalizing the charge carries so electron itinerant through the lattice suggested by other authors. Both calcium dopant concentration and the applied external magnetic field shows strong correlation in reduction of resistivity.« less

Spinel, YbFe2O4, and Yb2Fe3O7 types of structure for compounds in the In2O3 and Sc2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, Cu, or Zn) at temperatures over 1000C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimizuka, N.; Mohri, T.

In the Sc2O3-Ga2O3-CuO, Sc2O3-Ga2O3-ZnO, and Sc2O3-Al2O3-CuO systems, ScGaCuO4, ScGaZnO4, and ScAlCuO4 with the YbFe2O4-type structure and Sc2Ga2CuO7 with the Yb2Fe3O7-type structure were obtained. In the In2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO4, InGaNiO4, and InFeT MgO4 with the spinel structure, InGaZnO4, InGaMgO4, and InAl-CuO4 with the YbFe2O4-type structure, and In2Ga2MnO7 and In2Ga2ZnO7 with the Yb2Fe3O7-type structure were obtained. InGaMnO4 and InFe2O4 had both the YbFe2O4-type and spinel-type structures. The revised classification for the crystal structures of AB2O4 compounds is presented, based upon the coordination numbers of constituent A and B cations. 5more » references, 2 tables.« less

Influence of ionic liquids on the syntheses and structures of Mn(II) coordination polymers based on multidentate N-heterocyclic aromatic ligands and bridging carboxylate ligands.

PubMed

Qin, Jian-Hua; Wang, Hua-Rui; Pan, Qi; Zang, Shuang-Quan; Hou, Hongwei; Fan, Yaoting

2015-10-28

Seven Mn(ii) coordination polymers, namely {[Mn2(ptptp)Cl2(H2O)3]·H2O}n (1), {[Mn(μ-ptptp)3]2[Mn3(μ3-Cl)]2}·2Cl·16H2O (2), {[Mn2(ptptp)(ip)2(H2O)3]·H2O}n (3), {[Mn2(ptptp)(5-CH3-ip)2(H2O)3]·H2O}n (4), {[Mn4(ptptp)(5-Br-ip)3(H2O)3]·4H2O}n (5), {[Mn2(ptptp)(Hbtc)(H2O)2]·2H2O}n (6) and {[Mn2(ptptp)(tdc)(H2O)2]·1.5H2O}n (7), have been prepared based on multidentate N-heterocyclic aromatic ligands and bridging carboxylate ligands (H2ptptp = 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]pyridin-2-yl}-1H-1,2,4-triazol-3-yl)pyrazine; R-isophthalic acids, H2ip-R: R = -H (3), -CH3 (4), -Br (5); H3btc = trimesic acid (6); H2tdc = thiophene-2,5-dicarboxylic acid (7)), in order to further probe the multiple roles of [RMI]Br ionic liquids in the hydro/solvothermal synthesis (RMI = 1-alkyl-3-methylimidazolium, R = ethyl, or propyl, or butyl). The successful syntheses of complexes 2-6 suggest that in hydro/solvothermal synthesis the addition of a small amount of [RMI]Br plays a crucial role. Complex 1 exhibits single right-handed helices constructed by ptptp ligands and Mn(ii) ions. Complex 2 possesses octanuclear helicate structures in which two propeller-shaped [Mn(μ-ptptp)3](4-) units embrace two [Mn3(μ3-Cl)](5+) cluster cores inside. Complexes 3 and 4 are isostructural and display a 1D double chain formed by two kinds of pseudo meso-helices: (Mn-ptptp)n and (Mn-5-R-ip)n. Complex 5 has a 2D structure containing 1D Mn(ii) ion chains formed through carboxylates and [ptptp](2-)-N,N bridges. Complex 6 shows a 2D structure formed by a meso-helix (Mn-ptptp)n and the partly deprotonated Hbtc ligands. Complex 7 features a heterochiral [2 + 2] coaxially nested double-helical column formed by using the outer double-helices (Mn-ptptp)n as a template to encapsulate the inner double-helices (Mn-tdc)n with opposite orientation. All complexes were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography and powder X-ray diffraction. The magnetic properties of 1-7 were also investigated.

Hole doping and pressure effects on the II-II-V-based diluted magnetic semiconductor ( B a 1 - x K x ) ( Z n 1 - y M n y ) 2 A s 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, F.; Zhao, G. Q.; Escanhoela, Jr., C. A.

We investigate doping- and pressure-induced changes in the electronic state of Mn 3d and As 4p orbitals in II-II-V based diluted magnetic semiconductor (Ba 1-x,K x)(Zn 1-y,Mn y) 2As 2 to shed light into the mechanism of indirect exchange interactions leading to high ferromagnetic ordering temperature (T c = 230 K in optimally doped samples). A suite of x-ray spectroscopy experiments (emission, absorption and dichroism) show that the emergence, and further enhancement of ferromagnetic interactions with increased hole doping into the As 4p band is accompanied by a decrease in local 3d spin density at Mn sites. This is amore » result of increasing Mn 3d - As 4p hybridization with hole doping which enhances indirect exchange interactions between Mn dopants and gives rise to induced magnetic polarization in As 4p states. On the contrary, application of pressure suppresses exchange interactions. While Mn Kβ emission spectra show a weak response of 3d state to pressure, clear As 4p band broadening (hole delocalization) is observed under pressure ultimately leading to loss of ferromagnetism concomitant with a semiconductor to metal transition. The pressure response of As 4p and Mn 3d states is intimately connected with the evolution of the As-As interlayer distance and the geometry of the MnAs 4 tetrahedral units, which we probed with X-ray diffraction. Our results indicate that hole doping increases the degree of covalency between the anion (As) p states and cation (Mn) d states in the MnA s4 tetrahedron, a crucial ingredient to promote indirect exchange interactions between Mn dopants and high T c ferromagnetism. As a result, the instability of ferromagnetism and semiconducting state against pressure is mainly dictated by delocalization of anion p states.« less

Hole doping and pressure effects on the II-II-V-based diluted magnetic semiconductor ( B a 1 - x K x ) ( Z n 1 - y M n y ) 2 A s 2

DOE PAGES

Sun, F.; Zhao, G. Q.; Escanhoela, Jr., C. A.; ...

2017-03-13

We investigate doping- and pressure-induced changes in the electronic state of Mn 3d and As 4p orbitals in II-II-V based diluted magnetic semiconductor (Ba 1-x,K x)(Zn 1-y,Mn y) 2As 2 to shed light into the mechanism of indirect exchange interactions leading to high ferromagnetic ordering temperature (T c = 230 K in optimally doped samples). A suite of x-ray spectroscopy experiments (emission, absorption and dichroism) show that the emergence, and further enhancement of ferromagnetic interactions with increased hole doping into the As 4p band is accompanied by a decrease in local 3d spin density at Mn sites. This is amore » result of increasing Mn 3d - As 4p hybridization with hole doping which enhances indirect exchange interactions between Mn dopants and gives rise to induced magnetic polarization in As 4p states. On the contrary, application of pressure suppresses exchange interactions. While Mn Kβ emission spectra show a weak response of 3d state to pressure, clear As 4p band broadening (hole delocalization) is observed under pressure ultimately leading to loss of ferromagnetism concomitant with a semiconductor to metal transition. The pressure response of As 4p and Mn 3d states is intimately connected with the evolution of the As-As interlayer distance and the geometry of the MnAs 4 tetrahedral units, which we probed with X-ray diffraction. Our results indicate that hole doping increases the degree of covalency between the anion (As) p states and cation (Mn) d states in the MnA s4 tetrahedron, a crucial ingredient to promote indirect exchange interactions between Mn dopants and high T c ferromagnetism. As a result, the instability of ferromagnetism and semiconducting state against pressure is mainly dictated by delocalization of anion p states.« less

Effect of gadolinium dopant on structural, magneto-transport, magnetic and thermo-power of Pr0.8Sr0.2MnO3

NASA Astrophysics Data System (ADS)

Poojary, Thrapthi; Babu, P. D.; Sanil, Tejaswini; Daivajna, Mamatha D.

2018-07-01

In the present investigation structural, magneto-transport, magnetic and thermo-power measurements of Gadolinium (Gd) doped Pr0.8-xGdxSr0.2MnO3 (0, 0.2, 0.25 and 0.3) manganites have been done. All the samples are single phased with orthorhombic structure. Temperature variation of resistance exhibits a high temperature transition occurring at 156 K and a low temperature cusp at around 95 K for pristine sample. With Gd doping resistance behavior shows insulating behavior throughout the whole temperature range. Magneto-Resistance (MR%) increases with Gd doping. A huge increase in thermo-electric power is observed with Gd doping.

Interlinked multiphase Fe-doped MnO2 nanostructures: a novel design for enhanced pseudocapacitive performance

NASA Astrophysics Data System (ADS)

Wang, Ziya; Wang, Fengping; Li, Yan; Hu, Jianlin; Lu, Yanzhen; Xu, Mei

2016-03-01

Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g-1 even under a high mass loading (~5 mg cm-2). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm-3) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g-1. The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices.Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g-1 even under a high mass loading (~5 mg cm-2). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm-3) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g-1. The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08857g

Chemical trend of exchange coupling in diluted magnetic II-VI semiconductors: Ab initio calculations

NASA Astrophysics Data System (ADS)

Chanier, T.; Virot, F.; Hayn, R.

2009-05-01

We have calculated the chemical trend of magnetic exchange parameters ( Jdd , Nα , and Nβ ) of Zn-based II-VI semiconductors ZnA ( A=O , S, Se, and Te) doped with Co or Mn. We show that a proper treatment of electron correlations by the local spin-density approximation (LSDA)+U method leads to good agreement between experimental and theoretical values of the nearest-neighbor exchange coupling Jdd between localized 3d spins in contrast to the LSDA method. The exchange couplings between localized spins and doped electrons in the conduction band Nα are in good agreement with experiment as well. But the values for Nβ (coupling to doped holes in the valence band) indicate a crossover from weak coupling (for A=Te and Se) to strong coupling (for A=O ) and a localized hole state in ZnO:Mn. This hole localization explains the apparent discrepancy between photoemission and magneto-optical data for ZnO:Mn.

Superposition model analysis of zero field splitting for Mn2+ in some host single crystals

NASA Astrophysics Data System (ADS)

Bansal, R. S.; Ahlawat, P.; Bharti, M.; Hooda, S. S.

2013-07-01

The Newman superposition model has been used to investigate the substitution of Mn2+ for Zn2+ site in ammonium tetra flurozincate dihydrate and for Co2+ site in cobalt ammonium phosphate hexahydrate and cobalt potassium phosphate hexahydrate single crystals. The calculated values of zero field splitting parameter b 2 0 at room temperature fit the experimental data with average intrinsic parameters overline{b}2 (F) = -0.0531 cm-1 for fluorine and overline{b}2 (O) = -0.0280 cm-1 for oxygen, taken t 2 = 7 for Mn2+ doped in ammonium tetra fluorozincate dihydrate single crystals. The values of overline{b}2 determined for Mn2+ doped in cobalt ammonium phosphate hexahydrate are -0.049 cm-1 for site I and -0.045 cm-1 for site II and in cobalt pottasium phosphate hexahydrate single crystals it is found to be overline{b}2 = -0.086 cm-1. We find close agreement between theoretical and experimental values of b 2 0.

Preparation and Properties of (YCa)(TiMn)O3−δ Ceramics Interconnect of Solid Oxide Fuel Cells

PubMed Central

Liou, Yi-Cheng; Tsai, Wen-Chou; Yen, Hao-Hsuan; Chang, Yung-Chia

2015-01-01

(YCa)(TiMn)O3–δ ceramics prepared using a reaction-sintering process were investigated. Without any calcination involved, the mixture of raw materials was pressed and sintered directly. Y2Ti2O7 instead of YTiO3 formed when a mixture of Y2O3 and TiO2 with Y/Ti ratio 1/1 were sintered in air. Y2Ti2O7, YTiO2.085 and some unknown phases were detected in Y0.6Ca0.4Ti0.6Mn0.4O3–δ. Monophasic Y0.6Ca0.4Ti0.4Mn0.6O3–δ ceramics were obtained after 1400–1500 °C sintering. Dense Y0.6Ca0.4Ti0.4Mn0.6O3–δ with a density 4.69 g/cm3 was observed after 1500 °C/4 h sintering. Log σ for Y0.6Ca0.4Ti0.6Mn0.4O3–δ increased from –3.73 Scm–1 at 350 °C to –2.14 Scm–1 at 700 °C. Log σ for Y0.6Ca0.4Ti0.4Mn0.6O3–δ increased from –2.1 Scm–1 at 350 °C to –1.36 Scm–1 at 700 °C. Increasing Mn content decreased activation energy Ea and increased electrical conductivity. Reaction-sintering process is proved to be a simple and effective method to obtain (YCa)(TiMn)O3–δ ceramics for interconnects in solid oxide fuel cells. PMID:28793436

(La1-xSrx)0.98MnO3 perovskite with A-site deficiencies toward oxygen reduction reaction in aluminum-air batteries

NASA Astrophysics Data System (ADS)

Xue, Yejian; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

2017-02-01

The strontium doped Mn-based perovskites have been proposed as one of the best oxygen reduction reaction catalysts (ORRCs) to substitute the noble metal. However, few studies have investigated the catalytic activities of LSM with the A-site deficiencies. Here, the (La1-xSrx)0.98MnO3 (LSM) perovskites with A-site deficiencies are prepared by a modified solid-liquid method. The structure, morphology, valence state and oxygen adsorption behaviors of these LSM samples are characterized, and their catalytic activities toward ORR are studied by the rotating ring-disk electrode (RRDE) and aluminum-air battery technologies. The results show that the appropriate doping with Sr and introducing A-site stoichiometry can effectively tailor the Mn valence and increase the oxygen adsorption capacity of LSM. Among all the LSM samples in this work, the (La0.7Sr0.3)0.98MnO3 perovskite composited with 50% carbon (50%LSM30) exhibits the best ORR catalytic activity due to the excellent oxygen adsorption capacity. Also, this catalyst has much higher durability than that of commercial 20%Pt/C. Moreover, the maximum power density of the aluminum-air battery using 50%LSM30 as the ORRC can reach 191.3 mW cm-2. Our work indicates that the LSM/C composite catalysts with A-site deficiencies can be used as a promising ORRC in the metal-air batteries.

Rare earth doped zinc oxide varistors

DOEpatents

McMillan, April D.; Modine, Frank A.; Lauf, Robert J.; Alim, Mohammad A.; Mahan, Gerald D.; Bartkowiak, Miroslaw

1998-01-01

A varistor includes a Bi-free, essentially homogeneous sintered body of a ceramic composition including, expressed as nominal weight %, 0.2-4.0% oxide of at least one rare earth element, 0.5-4.0% Co.sub.3 O.sub.4, 0.05-0.4% K.sub.2 O, 0.05-0.2% Cr.sub.2 O.sub.3, 0-0.2% CaO, 0.00005-0.01% Al.sub.2 O.sub.3, 0-2% MnO, 0-0.05% MgO, 0-0.5% TiO.sub.3, 0-0.2% SnO.sub.2, 0-0.02% B.sub.2 O.sub.3, balance ZnO.

Electrochemical performances of LiMnPO4 synthesized from non-stoichiometric Li/Mn ratio.

PubMed

Xiao, Jie; Chernova, Natasha A; Upreti, Shailesh; Chen, Xilin; Li, Zheng; Deng, Zhiqun; Choi, Daiwon; Xu, Wu; Nie, Zimin; Graff, Gordon L; Liu, Jun; Whittingham, M Stanley; Zhang, Ji-Guang

2011-10-28

In this paper, the influences of the lithium content in the starting materials on the final performances of as-prepared Li(x)MnPO(4) (x hereafter represents the starting Li content in the synthesis step which does not necessarily mean that Li(x)MnPO(4) is a single phase solid solution in this work.) are systematically investigated. It has been revealed that Mn(2)P(2)O(7) is the main impurity when Li < 1.0 while Li(3)PO(4) begins to form once x > 1.0. The interactions between Mn(2)P(2)O(7) or Li(3)PO(4) impurities and LiMnPO(4) are studied in terms of the structural, electrochemical, and magnetic properties. At a slow rate of C/50, the reversible capacity of both Li(0.5)MnPO(4) and Li(0.8)MnPO(4) increases with cycling. This indicates a gradual activation of more sites to accommodate a reversible diffusion of Li(+) ions that may be related to the interaction between Mn(2)P(2)O(7) and LiMnPO(4) nanoparticles. Among all of the different compositions, Li(1.1)MnPO(4) exhibits the most stable cycling ability probably because of the existence of a trace amount of Li(3)PO(4) impurity that functions as a solid-state electrolyte on the surface. The magnetic properties and X-ray absorption spectroscopy (XAS) of the MnPO(4)·H(2)O precursor, pure and carbon-coated Li(x)MnPO(4) are also investigated to identify the key steps involved in preparing a high-performance LiMnPO(4). This journal is © the Owner Societies 2011

Morphological control of La0.7Sr0.3Co0.2Fe0.8O3-δ and La0.7Sr0.3MnO3-δ catalytic membrane using PEG-H2O additive

NASA Astrophysics Data System (ADS)

Iqbal, R. M.; Nurherdiana, S. D.; Hartanto, D.; Othman, M. H. D.; Fansuri, H.

2018-04-01

Methane is the primary combustible component in non condensable part of natural gas. It is a promising source for syngas (CO and H2) production by partial oxidation method. The conversion of methane to syngas by partial oxidation method needs a controlled amount of oxygen. Membrane which has asymmetric structure and selectively permeates oxygen can be used to supply just enough oxygen to the reaction. One pathway to the fabricate asymmetric membrane is phase inversion method with an addition of PEG to increase pore size. La0.7Sr0.3Co0.2Fe0.8O3-δ (LSCF 7328) and Laa0.7Sr0.3MnO3-δ (LSM 73) powder were synthesized by solid-state method and they were characterized by XRD. The green membrane was prepared by phase inversion method. A dope solution was made by mixing LSCF 7328 or LSM 73 powder with PEG and stirred them in NMP for 24 h. PESf was then added into the dope solution and the stirring was continued to another 24 h. The resulted dope solution was degassed by immersing the solution inside and conical flask in an ultrasonic bath to remove air bubbles. The degassed mixture was then casted by spreading it on a glass surface (with a thickness of 2 mm) followed by immersion in a water bath for 24 h to coagulate the degassed mixture. Membrane morphology was characterized by Scanning Electron Microscopy (SEM) while the decomposition temperature of the polymer binder was analyzed by Thermogravimetric Analyzer (TGA). The XRD results show that phase of LSCF 7328 and LSM 73 are similar to LaCoO3 and LaMnO3, respectively. It indicated that the perovskite synthesis was successful. SEM micrograph of membrane cross sections show that the green membrane have finger like pores and a dense layer. Pores also appear on top and bottom surface of the membrane. Based on TGA results, the highest weight lost of green membrane at 550-600°C which represents the decomposition of PESf binder.

Synthesis and loading-dependent characteristics of nitrogen-doped graphene foam/carbon nanotube/manganese oxide ternary composite electrodes for high performance supercapacitors.

PubMed

Cheng, Tao; Yu, Baozhi; Cao, Linli; Tan, Huiyun; Li, Xinghua; Zheng, Xinliang; Li, Weilong; Ren, Zhaoyu; Bai, Jinbo

2017-09-01

The ternary composite electrodes, nitrogen-doped graphene foam/carbon nanotube/manganese dioxide (NGF/CNT/MnO 2 ), have been successfully fabricated via chemical vapor deposition (CVD) and facile hydrothermal method. The morphologies of the MnO 2 nanoflakes presented the loading-dependent characteristics and the nanoflake thickness could also be tuned by MnO 2 mass loading in the fabrication process. The correlation between their morphology and electrochemical performance was systematically investigated by controlling MnO 2 mass loading in the ternary composite electrodes. The electrochemical properties of the flexible ternary electrode (MnO 2 mass loading of 70%) exhibited a high areal capacitance of 3.03F/cm 2 and a high specific capacitance of 284F/g at the scan rate of 2mV/s. Moreover, it was interesting to find that the capacitance of the NGF/CNT/MnO 2 composite electrodes showed a 51.6% increase after 15,000 cycles. The gradual increase in specific capacitance was due to the formation of defective regions in the MnO 2 nanostructures during the electrochemical cycles of the electrodes, which further resulted in increased porosity, surface area, and consequently increased electrochemical capacity. This work demonstrates a rarely reported conclusion about loading-dependent characteristics for the NGF/CNT/MnO 2 ternary composite electrodes. It will bring new perspectives on designing novel ternary or multi-structure for various energy storage applications. Copyright © 2017 Elsevier Inc. All rights reserved.

EPR investigation of local structure for [Mn(H 2O) 6] 2+ cluster in [M(H 2O) 6]XCl 6:Mn 2+ (M = Zn, Mg, Cd, Ca; X = Pt, Sn) systems at different temperatures

NASA Astrophysics Data System (ADS)

Tian, Wen-Yan; Kuang, Xiao-Yu; Li, Hui-Fang; Li, Yan-Fang; Ying-Li

2009-01-01

A theoretical method for studying the inter-relation between the local structure and EPR spectra is established by diagonalizing the complete energy matrices. For [M(H 2O) 6]XCl 6:Mn 2+ (M = Zn, Mg, Cd, Ca; X = Pt, Sn) systems, the calculated results demonstrate that the local structures around the octahedral Mn 2+ centers in the doped systems are very similar despite of the host crystals being different. Furthermore, it is shown that the EPR zero-field parameter D depends simultaneously on the local structure parameters R and θ while ( a - F) depends mainly on R, whether the doped systems are at liquid-nitrogen temperature or room temperature.

Influence of the dynamic lattice strain on the transport behavior of oxide heterojunctions

NASA Astrophysics Data System (ADS)

Wang, J.; Hu, F. X.; Chen, L.; Zhao, Y. Y.; Lu, H. X.; Sun, J. R.; Shen, B. G.

2013-01-01

All-perovskite oxide heterojunctions composed of electron-doped titanate LaxSr1 - xTiO3 (x = 0.1, 0.15) and hole-doped manganite La0.67Ca0.33MnO3 films were fabricated on piezoelectric substrate of (001)-0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-PT). Taking advantage of the excellent converse piezoelectric effect of PMN-PT, we investigated the influence of the dynamic lattice strain on transport properties of the heterojunctions by applying external bias electric fields on the PMN-PT substrate. Photovoltaic experiments were carried out to characterize the interfacial barrier of the heterojunction. A linear reduction in the barrier height was observed with the increase of the bias field applied on PMN-PT. The value of the barrier height reduces from ˜1.55 (˜1.30) to 1.02 (1.08) eV as the bias field increases from 0 to 12 kV/cm for the junction of La0.10Sr0.9TiO3/La0.67Ca0.33MnO3 (La0.15Sr0.85TiO3/La0.67Ca0.33MnO3). The observed dependency of barrier height on external field can be ascribed to the increasing release of trapped carriers by strain modulation, which results in a suppression of the depletion layer and increases the opportunity for electron tunneling across the depletion area.

Microstructures and superconducting properties of high performance MgB2 thin films deposited from a high-purity, dense Mg-B target.

PubMed

Li, G Z; Susner, M A; Bohnenstiehl, S D; Sumption, M D; Collings, E W

2015-12-01

High quality, c -axis oriented, MgB 2 thin films were successfully grown on 6H-SiC substrates using pulsed laser deposition (PLD) with subsequent in situ annealing. To obtain high purity films free from oxygen contamination, a dense Mg-B target was specially made from a high temperature, high pressure reaction of Mg and B to form large-grained (10~50 µm) MgB 2 . Microstructural analysis via electron microscopy found that the resulting grains of the film were composed of ultrafine columnar grains of 19-30 nm. XRD analysis showed the MgB 2 films to be c -axis oriented; the a -axis and c -axis lattice parameters were determined to be 3.073 ± 0.005 Å and 3.528 ± 0.010 Å, respectively. The superconducting critical temperature, T c,onset , increased monotonically as the annealing temperature was increased, varying from 25.2 K to 33.7 K. The superconducting critical current density as determined from magnetic measurements, J cm , at 5 K, was 10 5 A/cm 2 at 7.8 T; at 20 K, 10 5 A/cm 2 was reached at 3.1 T. The transport and pinning properties of these films were compared to "powder-in-tube" (PIT) and "internal-infiltration" (AIMI) processed wires. Additionally, examination of the pinning mechanism showed that when scaled to the peak in the pinning curve, the films follow the grain boundary, or surface, pinning mechanism quite well, and are similar to the response seen for C doped PIT and AIMI strands, in contrast to the behavior seen in undoped PIT wires, in which deviations are seen at high b ( b = B/B c2 ). On the other hand, the magnitude of the pinning force was similar for the thin films and AIMI conductors, unlike the values from connectivity-suppressed PIT strands.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phan, The-Long; Jung, C. U.; Lee, B. W., E-mail: bwlee@hufs.ac.kr

We prepared orthorhombic La{sub 0.7−x}Y{sub x}Ca{sub 0.3}MnO{sub 3} samples (x = 0, 0.04, 0.06, and 0.08) by conventional solid-state reaction and then studied their magnetic properties and magnetocaloric (MC) effect based on magnetization versus temperature and magnetic-field measurements, M(T, H). The experimental results revealed that an x increase in La{sub 0.7−x}Y{sub x}Ca{sub 0.3}MnO{sub 3} reduced the ferromagnetic-paramagnetic transition temperature (T{sub C}) from 260 K (for x = 0) to ∼126 K (for x = 0.08). Around the T{sub C}, maximum magnetic-entropy changes for a magnetic-field variation interval H = 50 kOe are about 10.7, 8.5, 7.4, and 5.8 J·kg{sup −1}·K{sup −1} for x = 0, 0.04, 0.06, and 0.08, respectively, corresponding to refrigerantmore » capacities RC = 250–280 J·kg{sup −1}. These values are comparable to those of some conventional MC materials, revealing the applicability of La{sub 0.7−x}Y{sub x}Ca{sub 0.3}MnO{sub 3} in magnetic refrigeration. Using the Arrott method and scaling hypothesis as analyzing high-field M(H, T) data, and the universal-curve construction of the magnetic entropy change, we found a magnetic-phase separation. While the samples x = 0−0.06 exhibit a first-order magnetic phase transition, x = 0.08 exhibits the crossover of the first-to-second-order phase transformation (with its critical-exponent values close to those expected for the tricritical mean-field theory) and has the presence of ferromagnetic clusters even above the T{sub C}. Such the variations in the magnetism and MC effect are related to the changes in structural parameters caused by the Y substitution for La because Y doping does not change the concentration ratio of Mn{sup 3+}/Mn{sup 4+}.« less

Pyroxenoids of pyroxmangite-pyroxferroite series from xenoliths of Bellerberg paleovolcano (Eifel, Germany): Chemical variations and specific features of cation distribution

NASA Astrophysics Data System (ADS)

Shchipalkina, N. V.; Aksenov, S. M.; Chukanov, N. V.; Pekov, I. V.; Rastsvetaeva, R. K.; Schäfer, C.; Ternes, B.; Shüller, W.

2016-11-01

The pyroxferroite and pyroxmangite from xenoliths of aluminous gneisses in the alkaline basalts of Bellerberg paleovulcano (Eifel, Germany) have been studied by electron-probe and X-ray diffraction methods and IR spectroscopy. The parameters of the triclinic unit cells are found to be a = 6.662(1) Å, b = 7.525(1) Å, c = 15.895(2) Å, α = 91.548(3)°, β = 96.258(3)°, and γ = 94.498(3)° for pyroxferroite and a = 6.661(3) Å, b = 7.513(3) Å, c = 15.877(7) Å, α = 91.870(7)°, β = 96.369(7)°, and γ = 94.724(7)° for pyroxmangite; sp. gr. Poverline 1 . The crystallochemical formulas ( Z = 2) are, respectively, M(1-2)(Mn0.5Ca0.4Na0.1)2 M(3-6)(Fe, Mn)4 M7[Mg0.6(Fe, Mn)0.4][Si7O21] and M(1-3)(Mn, Fe)3 M(4-6)[(Fe, Mn)0.7Mg0.3]3 M7[Mg0.5(Fe, Mn)0.5][Si7O21]. For these and previously studied representatives of the pyroxmangite structural type, an analysis of the cation distribution over sites indicates wide isomorphism of Mn2+, Fe2+, and Mg in all cation M(1-7) sites and the preferred incorporation of Ca and Na into large seven-vertex M1O7 and M2O7 polyhedra and Mg into the smallest five-vertex M7O5 polyhedron.

Cosubstitution effect on the magnetic, transport, and thermoelectric properties of the electron-doped perovskite manganite CaMnO3

NASA Astrophysics Data System (ADS)

Okuda, T.; Fujii, Y.

2010-11-01

We have investigated magnetic, transport, and thermoelecric properties of polycrystalline Ca1-xSrxMn1-yMoyO3, and have tried to optimize the n-type thermoelectric response below room temperature. The Sr substitution enlarges a Mn-O-Mn bond angle and increases a crystal symmetry, which enhances one electron transfer of the electrons doped by the Mo substitution. This effect promotes the competition between correlations of a G-type antiferromagnetic (AF) order and a C-type AF order accompanying a 3d3z2-r2 orbital order, leading to the more complicated magnetic phase diagram of Ca0.75Sr0.25Mn1-yMoyO3 than that of CaMn1-yMoyO3. A subtle balance between the effects of the enhanced one electron transfer and the introduced disorder into the A(Ca)-site upon the transport properties enhances a dimensionless thermoelectric figure-of-merit ZT up to 0.03 at room temperature. However, a correlation of the 3d3z2-r2 orbital order is also promoted by the Sr substitution, which bounds a further enhancement of ZT.

Effects of doping on ferroelectric properties and leakage current behavior of KNN-LT-LS thin films on SrTiO3 substrate

NASA Astrophysics Data System (ADS)

Abazari, M.; Safari, A.

2009-05-01

We report the effects of Ba, Ti, and Mn dopants on ferroelectric polarization and leakage current of (K0.44Na0.52Li0.04)(Nb0.84Ta0.1Sb0.06)O3 (KNN-LT-LS) thin films deposited by pulsed laser deposition. It is shown that donor dopants such as Ba2+, which increased the resistivity in bulk KNN-LT-LS, had an opposite effect in the thin film. Ti4+ as an acceptor B-site dopant reduces the leakage current by an order of magnitude, while the polarization values showed a slight degradation. Mn4+, however, was found to effectively suppress the leakage current by over two orders of magnitude while enhancing the polarization, with 15 and 23 μC/cm2 remanent and saturated polarization, whose values are ˜70% and 82% of the reported values for bulk composition. This phenomenon has been associated with the dual effect of Mn4+ in KNN-LT-LS thin film, by substituting both A- and B-site cations. A detailed description on how each dopant affects the concentrations of vacancies in the lattice is presented. Mn-doped KNN-LT-LS thin films are shown to be a promising candidate for lead-free thin films and applications.

Hole doping and pressure effects on the II-II-V-based diluted magnetic semiconductor (B a1 -xKx ) (Zn1-yM ny ) 2A s2

NASA Astrophysics Data System (ADS)

Sun, F.; Zhao, G. Q.; Escanhoela, C. A.; Chen, B. J.; Kou, R. H.; Wang, Y. G.; Xiao, Y. M.; Chow, P.; Mao, H. K.; Haskel, D.; Yang, W. G.; Jin, C. Q.

2017-03-01

We investigate doping- and pressure-induced changes in the electronic state of Mn 3 d and As 4 p orbitals in II-II-V-based diluted magnetic semiconductor (B a1 -xKx ) (Zn1-yM ny ) 2A s2 to shed light into the mechanism of indirect exchange interactions leading to high ferromagnetic ordering temperature (T c =230 K in optimally doped samples). A suite of x-ray spectroscopy experiments (emission, absorption, and dichroism) show that the emergence and further enhancement of ferromagnetic interactions with increased hole doping into the As 4 p band is accompanied by a decrease in local 3 d spin density at Mn sites. This is a result of increasing Mn 3 d -As 4 p hybridization with hole doping, which enhances indirect exchange interactions between Mn dopants and gives rise to induced magnetic polarization in As 4 p states. On the contrary, application of pressure suppresses exchange interactions. While Mn K β emission spectra show a weak response of 3 d states to pressure, clear As 4 p band broadening (hole delocalization) is observed under pressure, ultimately leading to loss of ferromagnetism concomitant with a semiconductor to metal transition. The pressure response of As 4 p and Mn 3 d states is intimately connected with the evolution of the As-As interlayer distance and the geometry of the MnA s4 tetrahedral units, which we probed with x-ray diffraction. Our results indicate that hole doping increases the degree of covalency between the anion (As) p states and cation (Mn) d states in the MnA s4 tetrahedron, a crucial ingredient to promote indirect exchange interactions between Mn dopants and high T c ferromagnetism. The instability of ferromagnetism and semiconducting states against pressure is mainly dictated by delocalization of anion p states.

Syntheses, structures, and magnetic properties of three new MnII-[MoIII(CN)7]4- molecular magnets.

PubMed

Wei, Xiao-Qin; Pi, Qian; Shen, Fu-Xing; Shao, Dong; Wei, Hai-Yan; Wang, Xin-Yi

2018-05-22

By reaction of K4[MoIII(CN)7]·2H2O, Mn(ClO4)2·6H2O and bidentate chelating ligands, three new cyano-bridged compounds, namely Mn2(3-pypz)(H2O)(CH3CN)[Mo(CN)7] (1), Mn2(1-pypz)(H2O)(CH3CN)[Mo(CN)7] (2) and Mn2(pyim)(H2O)(CH3CN)[Mo(CN)7] (3) (3-pypz = 2-(1H-pyrazol-3-yl)pyridine, 1-pypz = 2-(1H-pyrazol-1-yl)pyridine, pyim = 2-(1H-imidazol-2-yl)pyridine), have been synthesized and characterized structurally and magnetically. Single crystal X-ray analyses revealed that although the chelating ligands are different, compounds 1 to 3 are isomorphous and crystallize in the same monoclinic space group C2/m. Connected by the bridging cyano groups, one crystallographically unique [Mo(CN)7]4- unit and three crystallographically unique MnII ions of different coordination environments form similar three-dimensional frameworks, which have a four-nodal 3,4,4,7-connecting topological net with a vertex symbol of {43}{44·62}2{410·611}. Magnetic measurements revealed that compounds 1-3 display long-range magnetic ordering with critical temperatures of 64, 66 and 62 K, respectively. These compounds are rare examples of a small number of chelating co-ligand coordinated [Mo(CN)7]4--based magnetic materials. Specifically, the bidentate chelating ligands were successfully introduced into the heptacyanomolybdate system for the first time.

In-situ Raman spectroscopic investigation of LiMn1.45Ni0.45M0.1O4 (M = Cr, Co) 5 V cathode materials

NASA Astrophysics Data System (ADS)

Zhu, W.; Liu, D.; Trottier, J.; Gagnon, C.; Howe, J.; Mauger, A.; Julien, C. M.; Zaghib, K.

2015-12-01

In-situ Raman spectroscopy is employed to investigate the valence state variations of nickel and manganese, as well as the local structure change of LiMn1.45Ni0.45M0.1O4 (M = Cr, Co) cathodes (LMN) during galvanostatic charge-discharge. Raman spectra are collected between 3.5 and 4.9 V in the wave number range of 100-800 cm-1. The Raman observations showed that the pristine cathodes of Cr- and Co-doped LMN have essentially the same spectra, and they also have similar evolution patterns during cycling showing their reversible behaviour in the de-lithiation and lithiation processes. The Raman spectra of the pristine cathodes have eleven bands, located at 162, 220, 378, 408, 486, 498, 528, 593, 613, 639 and 672 cm-1. The bands with wave number <300 cm-1 are attributed to the translation mode of molecular vibration; the 486, 593 and 639 cm-1 bands are assigned to the stretching mode of Mn-O bond; and the vibration modes at 408, 498, 528 and 613 cm-1 originated from the Ni-O bond; The band at 672 cm-1 is attributed to A1g mode of Cr3+-O/Co3+-O. During cycling, several new bands are detected near the end of charge, among which the T2g(T) band at 170 cm-1 is attributed to the translation mode of lattice vibration in which the lithium concentration is low, and the T2g band at 538 cm-1 is due to the presence of Ni4+-O bond in the crystal structure. The T2g(T) and T2g(Ni4+-O) bands are clearly evident at V ≥ 4.78 (x ∼ 0.32) and V ≥ 4.82 (x ∼ 0.28) for Cr- and Co-doped LMN, respectively.

Effect of magnetic field on the flux pinning mechanisms in Al and SiC co-doped MgB2 superconductor

NASA Astrophysics Data System (ADS)

Kia, N. S.; Ghorbani, S. R.; Arabi, H.; Hossain, M. S. A.

2018-07-01

MgB2 superconductor samples co-doped with 0.02 wt. Al2O3 and 0-0.05 wt. SiC were studied by magnetization - magnetic field (M-H) loop measurements at different temperatures. The critical current density has been calculated by the Bean model, and the irreversibility field, Hirr, has been obtained by the Kramer method. The pinning mechanism of the co-doped sample with 2% Al and 5% SiC was investigated in particular due to its having the highest Hirr. The normalized volume pinning force f = F/Fmax as a function of reduced magnetic field h = H/Hirr has been obtained, and the pinning mechanism was studied by the Dew-Houghes model. It was found that the normal point pinning (NPP), the normal surface pinning (NSP), and the normal volume pinning (NVP) mechanisms play the main roles. The magnetic field and temperature dependence of contributions of the NPP, NSP, and NVP pinning mechanisms were obtained. The results show that the contributions of the pinning mechanisms depend on the temperature and magnetic field. From the temperature dependence of the critical current density within the collective pinning theory, it was found that both the δl pinning due to spatial fluctuations of the charge-carrier mean free path and the δTc pinning due to randomly distributed spatial variations in the transition temperature coexist at zero magnetic field in co-doped samples. Yet, the charge-carrier mean-free-path fluctuation pinning (δl) is the only important pinning mechanism at non-zero magnetic fields.

New Defective Brannerite-Type Vanadates. I. Synthesis and Study of Mn 1- x- yφ xNa yV 2-2 x-yMo 2 x+yO 6 Solid Solutions

NASA Astrophysics Data System (ADS)

Masłowska, Bogna; Ziółkowski, Jacek

1994-05-01

MnV 2O 6 of the brannerite-type structure (below 540°C) doped with MoO 3 and Na 2O forms isomorphous solid solutions MnNaφ = Mn 1- x-yφ xNa yV 2-2 x-yMo 2 x+ yO 6 (φ cation vacancy in the original Mn position), belonging to the pseudoternary MnV 2O 6-NaVMoO 6-MoO 3 system. Particular cases are MnNa = Mn 1- yNa y V 2- yMo yO 6 ( x = 0), Mnφ = Mn 1- xφ xV 2-2 xMo 2 xO 6 ( y = 0), and Naφ = Na 1- xφ xV 1- xMo 1+ xO 6 ( x + y = 1). MnV 2O 6 and NaVMoO 6 show miscibility in the entire composition range (MnNa). The opposite boundary of MnNaφ passes through the (100 x, 100 y) points (45, 0), (33, 30), and (30, 70). The phase diagram of the pseudobinary MnV 2O 6-NaVMoO 6 system (determined with DTA) shows (i) a narrow double-lens-type solidus-liquidus gap at high values of y , (ii) two peritectic meltings at lower y (yielding the high temperature β-MnNa and Mn 2V 2O 7), and (iii) little area of β-MnNa. Lattice parameters of MnNa (determined with X-ray diffraction) reveal small deviations from Vegard's law. As the ionic radii of both dopants (Na + and Mo 6+) are, respectively, larger than those of mother ions (Mn 2+ and V 5+), the unit cell increases in all directions with rising y along the MnNa series of solid solutions. However, due to the anisotropy of the structure, parameter c is strongly sensitive to Na/Mn substitution, b is ruled by Mo/V, and a is weakly influenced by Mo/V. Close analogy to the behavior of the previously studied MnV 2O 6-LiVMoO 6-MoO 6 system is discussed.

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE PAGES

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan; ...

2017-03-20

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Low Temperature Specific Heat in Lightly Mn-Substituted Electron-Doped SrTiO3

NASA Astrophysics Data System (ADS)

Okuda, Tetsuji; Hata, Hiroto; Eto, Takahiro; Sobaru, Shogo; Oda, Ryosuke; Noda, Masaaki; Kuwahara, Hideki

2017-08-01

We found large changes in the low-temperature specific heat (low-T C) in the lightly Mn-substituted electron-doped perovskites Sr0.95La0.05Ti1-yMnzO3 with y = 0.02 and 0.04 by applying magnetic fields up to 9 T. The changes in the low-T C are qualitatively well explained by the Schottky specific heat (CSch) of localized spins of the Mn 3d electrons in weak internal magnetic fields via itinerant electrons. However, the actual numbers of localized spins estimated from CSch are about 30% smaller than the expected values. Part of the localized spins of the Mn 3d electrons may disappear due to Kondo coupling with the itinerant electrons.

Three-dimensional reduced-graphene/MnO2 prepared by plasma treatment as high-performance supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Liu, Runru; Wen, Dongdong; Zhang, Xueyu; Wang, Dejun; Yang, Qiang; Yuan, Beilei; Lü, Wei

2018-06-01

In this work, three-Dimensional nitrogen-doped graphene/MnO2 (NG/MnO2) was prepared by plasma treatment, which provides a high specific surface area due to porous structure and exhibits enhanced supercapacitor performance. The advantage of NG/MnO2 electrode was obvious compared with reduced graphene oxide/MnO2 (RGO/MnO2) which was prepared by traditional hydrothermal method, such as improved electrochemical property and better cycling stability. The specific capacitance of NG/MnO2 at the scan rate of 5 mV s‑1 (393 F g‑1) is higher than that of RGO/MnO2 (260 F g‑1). In addition, NG/MnO2 showed higher durability with 90.2% capacitance retention than that of RGO/MnO2 (82%) after 5000 cycles. Such cheap and high-performance supercapacitor electrodes are available by our feasible plasma treatment, which give promise in large-scale commercial energy storage devices.

Photoluminescence and afterglow luminescence properties of a green-emitting Na2BeGeO4:Mn2+ phosphor

NASA Astrophysics Data System (ADS)

Lu, Jie; Shen, Linjiang

2018-07-01

Recently, developing free rare-earth (RE) doped afterglow phosphors has received great attentions in the lighting field. In this work, we prepare and report a RE-free phosphor, Na2BeGeO4:Mn2+, which can simultaneously emit the green fluorescence and afterglow luminescence upon excitation at UV light. Our results reveal that the as-prepared samples crystallize in orthorhombic type with the space group of Pmn21 (31). The green emission is a broad band centered at 525 nm, corresponds to the 4T1(4G)-6A1(6S) transition of Mn2+ ions. After exposing to a 254 nm UV lamp for 10 min, the green afterglow luminescence seen with naked eyes can last more than 5 h. Together with the structural analysis and thermoluminescence (TL) spectra, the afterglow luminescence mechanism is also discussed in this work.

Co-Precipitation Synthesis and Optical Properties of Mn4+-Doped Hexafluoroaluminate w-LED Phosphors

PubMed Central

Geitenbeek, Robin G.; Meijerink, Andries

2017-01-01

Mn4+-activated hexafluoroaluminates are promising red-emitting phosphors for white light emitting diodes (w-LEDs). Here, we report the synthesis of Na3AlF6:Mn4+, K3AlF6:Mn4+ and K2NaAlF6:Mn4+ phosphors through a simple two-step co-precipitation method. Highly monodisperse large (~20 μm) smoothed-octahedron shaped crystallites are obtained for K2NaAlF6:Mn4+. The large size, regular shape and small size distribution are favorable for application in w-LEDs. All Mn4+-doped hexafluoroaluminates show bright red Mn4+ luminescence under blue light excitation. We compare the optical properties of Na3AlF6:Mn4+, K3AlF6:Mn4+ and K2NaAlF6:Mn4+ at room temperature and 4 K. The luminescence measurements reveal that multiple Mn4+ sites exist in M3AlF6:Mn4+ (M = Na, K), which is explained by the charge compensation that is required for Mn4+ on Al3+ sites. Thermal cycling experiments show that the site distribution changes after annealing. Finally, we investigate thermal quenching and show that the luminescence quenching temperature is high, around 460–490 K, which makes these Mn4+-doped hexafluoroaluminates interesting red phosphors for w-LEDs. The new insights reported on the synthesis and optical properties of Mn4+ in the chemically and thermally stable hexafluoroaluminates can contribute to the optimization of red-emitting Mn4+ phosphors for w-LEDs. PMID:29149083

A green approach for single-pot synthesis of graphene oxide and its composite with Mn3O4

NASA Astrophysics Data System (ADS)

Rathour, Rishi Karan Singh; Bhattacharya, Jayanta

2018-04-01

Development of simple, environment friendly and effective approaches for the synthesis of graphene oxide (GO) is highly demanded because of its widespread applications. The present study focuses on synthesis of GO coupled with simultaneous conversion of waste byproduct as novel products, which was further used to synthesize Mn3O4 nanoparticle (Mn3O4NP), composite of GO with Mn3O4NP (rGO-Mn3O4NC) and high purity K2SO4 crystal. The characterization of GO, Mn3O4NP, and rGOMn3O4NC demonstrates the formation of single layer ∼2 μm lateral GO, ∼15 nm sized Mn3O4NP, and thermally stable rGO-Mn3O4NC. The experimental yields of GO, Mn3O4NP, and K2SO4 were 1.72, 2.04, and 87.0 g from 1.0, 4.0g, and 25.0mL of graphite, KMnO4, and H2SO4. The specific surface area of GO, Mn3O4NP, and rGO-Mn3O4NC were found to be 152.5, 233, and 27.6 m2/g, respectively. The adsorptive removal of lead (Pb2+) and methylene blue (MB) from aqueous solution by GO, Mn3O4NP, and rGO-Mn3O4NC shows an adsorption capacity of 42.3, 219, and 105 mg/g, for Pb2+ and 366, 7.5, and 17.5 mg/g, for MB, respectively. The cost analysis reveals that the proposed synthesis route is comparatively quite competitive.

Facile synthesis of highly uniform Mn/Co-codoped ZnO nanowires: optical, electrical, and magnetic properties.

PubMed

Li, Huifeng; Huang, Yunhua; Zhang, Qi; Qiao, Yi; Gu, Yousong; Liu, Jing; Zhang, Yue

2011-02-01

In this article, Co/Mn-codoped ZnO nanowires (NWs) were successfully synthesized on a silicon substrate by the thermal evaporation method with Au catalyst. The X-ray diffraction pattern indicated that the Co/Mn-codoped ZnO NWs are a hexagonal wurtzite structure without a second phase, and energy dispersive X-ray spectroscopy revealed that the Co and Mn ions were introduced into the ZnO NWs with the content of ∼0.8 at% and ∼1.2 at%, respectively. Photoluminescence spectra and Raman spectra showed that the Co/Mn were doped into the NWs and resulted in the shift of the near-band-edge emission. Moreover, the novel Raman peak at 519.3 cm(-1) has suggested that the two kinds of cations via doping could affect the local polarizability. Compared with the undoped ZnO NW, the electrical measurement showed that the Co/Mn-codoping enhanced the conductivity by an order of magnitude due to the presence of Co, Mn cations. The electron mobility and carrier concentration of a fabricated field effect transistor (FET) device is 679 cm2 V(-1) s(-1) and 2×10(18) cm(-3), respectively. Furthermore, the M-H curve demonstrated that the Co/Mn-codoped ZnO NWs have obvious ferromagnetic characteristics at room temperature. Our study enhances the understanding of the novel performances of transition-metal codoped ZnO NWs and also provides a potential way to fabricate optoelectronic devices.

Superconductor to Mott insulator transition in YBa2Cu3O7/LaCaMnO3 heterostructures.

PubMed

Gray, B A; Middey, S; Conti, G; Gray, A X; Kuo, C-T; Kaiser, A M; Ueda, S; Kobayashi, K; Meyers, D; Kareev, M; Tung, I C; Liu, Jian; Fadley, C S; Chakhalian, J; Freeland, J W

2016-09-15

The superconductor-to-insulator transition (SIT) induced by means such as external magnetic fields, disorder or spatial confinement is a vivid illustration of a quantum phase transition dramatically affecting the superconducting order parameter. In pursuit of a new realization of the SIT by interfacial charge transfer, we developed extremely thin superlattices composed of high Tc superconductor YBa2Cu3O7 (YBCO) and colossal magnetoresistance ferromagnet La0.67Ca0.33MnO3 (LCMO). By using linearly polarized resonant X-ray absorption spectroscopy and magnetic circular dichroism, combined with hard X-ray photoelectron spectroscopy, we derived a complete picture of the interfacial carrier doping in cuprate and manganite atomic layers, leading to the transition from superconducting to an unusual Mott insulating state emerging with the increase of LCMO layer thickness. In addition, contrary to the common perception that only transition metal ions may respond to the charge transfer process, we found that charge is also actively compensated by rare-earth and alkaline-earth metal ions of the interface. Such deterministic control of Tc by pure electronic doping without any hindering effects of chemical substitution is another promising route to disentangle the role of disorder on the pseudo-gap and charge density wave phases of underdoped cuprates.

Contrasting conduction mechanisms of two internal barrier layer capacitors: (Mn, Nb)-doped SrTiO3 and CaCu3Ti4O12

NASA Astrophysics Data System (ADS)

Tsuji, Kosuke; Chen, Wei-Ting; Guo, Hanzheng; Lee, Wen-Hsi; Guillemet-Fritsch, Sophie; Randall, Clive A.

2017-02-01

The d.c. conduction is investigated in the two different types of internal barrier layer capacitors, namely, (Mn, Nb)-doped SrTiO3 (STO) and CaCu3Ti4O12 (CCTO). Scanning electron microscopy (SEM) and Capacitance - Voltage (C-V) analysis are performed to estimate the effective electric field at a grain boundary, EGB. Then, the d.c. conduction mechanism is discussed based on the J (Current density)-EGB characteristics. Three different conduction mechanisms are successively observed with the increase of EGB in both systems. In (Mn, Nb)-doped STO, non-linear J-EGB characteristics is temperature dependent at the intermediate EGB and becomes relatively insensitive to the temperature at the higher EGB. The J- EGB at each regime is explained by the Schottky emission (SE) followed by Fowler-Nordheim (F-N) tunneling. Based on the F-N tunneling, the breakdown voltage is then scaled by the function of the depletion layer thickness and Schottky barrier height at the average grain boundary. The proposed function shows a clear linear relationship with the breakdown. On the other hand, F-N tunneling was not observed in CCTO in our measurement. Ohmic, Poole-Frenkel (P-F), and SE are successively observed in CCTO. The transition point from P-F and SE depends on EGB and temperature. A charge-based deep level transient spectroscopy study reveals that 3 types of trap states exist in CCTO. The trap one with Et ˜ 0.65 eV below the conduction band is found to be responsible for the P-F conduction.

Coating magnetic CuFe2O4 nanoparticles with OMS-2 for enhanced degradation of organic pollutants via peroxymonosulfate activation

NASA Astrophysics Data System (ADS)

Ye, Peng; Wu, Deming; Wang, Manye; Wei, Yi; Xu, Aihua; Li, Xiaoxia

2018-01-01

A heterogeneous magnetic CuFe2O4@OMS-2 catalyst was fabricated through a facile solvent-free process using Mn(CH3COO)2 and KMnO4 in the presence of CuFe2O4. It was found that the BET surface area of OMS-2 as well as the ratio of low-valent manganese species significantly increased in the hybrid catalyst, due to interactions between CuFe2O4 and the precursor of amorphous manganese oxide. Acid Orange 7 (AO7) and other organic pollutants could be completely degraded by the CuFe2O4@OMS-2 catalyst within 30 min in the presence of peroxymonosulfate (PMS), while CuFe2O4 and OMS-2 showed no significant activity for the reaction. The hybrid catalyst also exhibited excellent long-term stability and could be easily recovered with the assistance of an external magnetic field. A possible degradation mechanism for the synergistic effects of different valent metal species and reactive radicals was proposed, which involved the electron transfer from Mn(III) or Mn(II) species to PMS with the generation of sulfate and hydroxyl radicals, and from AO7 and Cu(I) in CuFe2O4 to Mn(IV) and Mn(III) to reduce these Mn species.

Flexible Fe3O4@Carbon Nanofibers Hierarchically Assembled with MnO2 Particles for High-Performance Supercapacitor Electrodes.

PubMed

Iqbal, Nousheen; Wang, Xianfeng; Babar, Aijaz Ahmed; Zainab, Ghazala; Yu, Jianyong; Ding, Bin

2017-11-09

Increasing use of wearable electronic devices have resulted in enhanced demand for highly flexible supercapacitor electrodes with superior electrochemical performance. In this study, flexible composite membranes with electrosprayed MnO 2 particles uniformly anchored on Fe 3 O 4 doped electrospun carbon nanofibers (Fe 3 O 4 @CNF Mn ) have been prepared as flexible electrodes for high-performance supercapacitors. The interconnected porous beaded structure ensures free movement of electrolyte within the composite membranes, therefore, the developed supercapacitor electrodes not only offer high specific capacitance of ~306 F/g, but also exhibit good capacitance retention of ~85% after 2000 cycles, which certify that the synthesized electrodes offer high and stable electrochemical performance. Additionally, the supercapacitors fabricated from our developed electrodes well maintain their performance under flexural stress and exhibit a very minute change in specific capacitance even up to 180° bending angle. The developed electrode fabrication strategy integrating electrospinning and electrospray techniques paves new insights into the development of potential functional nanofibrous materials for light weight and flexible wearable supercapacitors.

Radiation-induced defects in manganese-doped lithium tetraborate phosphor.

PubMed

Annalakshmi, O; Jose, M T; Madhusoodanan, U; Sridevi, J; Venkatraman, B; Amarendra, G; Mandal, A B

2015-01-01

Lithium tetraborate doped with manganese synthesised by solid-state sintering technique exhibits a dosimetric peak at 280°C. The high-temperature glow curve results in no fading for three months. The sensitivity of Li2B4O7:Mn is determined to be 0.9 times that of TLD-100. The infrared spectrum of this phosphor indicates the presence of bond vibrations corresponding to BO4 tetrahedral and BO3 triangles. The mechanism for thermoluminescence in this phosphor was proposed based on the thermoluminescence (TL) emission spectra, kinetic analysis of TL glow curves and electron paramagnetic resonance (EPR) measurements on non-irradiated and gamma-irradiated phosphors. It was identified that oxygen vacancies and Boron oxygen hole centre (BOHC) are the electron and hole trap centres for TL in this phosphor. When the phosphor is heated, the electrons are released from the electron trap and recombine with the trapped holes. The excitation energy during the recombination is transferred to the nearby Mn(2+) ions, which emit light at 580 nm. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Non-aqueous solution preparation of doped and undoped Li{sub x}Mn{sub y}O{sub z}

DOEpatents

Boyle, T.J.; Voigt, J.A.

1997-05-20

A method is described for generation of phase-pure doped and undoped Li{sub x}Mn{sub y}O{sub z} precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder. 1 fig.

Structural, morphological, magnetic and dielectric characterization of nano-phased antimony doped manganese zinc ferrites

NASA Astrophysics Data System (ADS)

Sridhar, Ch. S. L. N.; Lakshmi, Ch. S.; Govindraj, G.; Bangarraju, S.; Satyanarayana, L.; Potukuchi, D. M.

2016-05-01

Nano-phased doped Mn-Zn ferrites, viz., Mn0.5-x/2Zn0.5-x/2SbXFe2O4 for x=0 to 0.3 (in steps of 0.05) prepared by hydrothermal method are characterized by X-ray diffraction, Infrared and scanning electron microscopy. XRD and SEM infer the growth of nano-crystalline cubic and hematite (α-Fe2O3) phase structures. IR reveals the ferrite phase abundance and metal ion replacement with dopant. Decreasing trend of lattice constant with dopant reflects the preferential replacement of Fe3+ions by Sb5+ion. Doping is found to cause for the decrease (i.e., 46-14 nm) of grain size. An overall trend of decreasing saturation magnetization is observed with doping. Low magnetization is attributed to the diamagnetic nature of dopant, abundance of hematite (α-Fe2O3) phase, non-stoichiometry and low temperature (800 °C) sintering conditions. Increasing Yafet-Kittel angle reflects surface spin canting to pronounce lower Ms. Lower coercivity is observed for x≤0.1, while a large Hc results for higher concentrations. High ac resistivity (~106 ohm-cm) and low dielectric loss factor (tan δ~10-2-10-3) are witnessed. Resistivity is explained on the base of a transformation in the Metal Cation-to-Oxide anion bond configuration and blockade of conductivity path. Retarded hopping (between adjacent B-sites) of carriers across the grain boundaries is addressed. Relatively higher resistivity and low dielectric loss in Sbdoped Mn-Zn ferrite systems pronounce their utility in high frequency applications.

Formation of (FexMn(2-x))O3 solid solution and high sulfur capacity properties of Mn-based/M41 sorbents for hot coal gas desulfurization.

PubMed

Zhang, Y; Liu, B S; Zhang, F M; Zhang, Z F

2013-03-15

Several MCM-41 materials were synthesized at different conditions by hydrothermal procedure using cheap and easily available industrial water glass as silica source. Fe doped manganese-based oxide/MCM-41 sorbents were prepared by a sol-gel method. The effects of loadings of metal oxide, Fe/Mn molar ratios over MCM-41 and reaction temperature on the performance of sorbent for hot coal gas desulfurization were investigated. Various techniques such as BET, XRD, XPS, LRS and HRTEM were used to characterize the sorbents. The result indicated Fe(3+) ions could occupy a position of Mn(3+) in cubic lattice of Mn2O3 and the (FexMn2-x)O3 solid solution is mainly active phase of sorbent. Moreover, the result of nine successive sulfurization-regeneration cycles of sorbent showed high sulfur adsorption capacity and endurable stability of FeMn4Ox/MCM-41 for H2S removal. Copyright © 2013 Elsevier B.V. All rights reserved.

Effects of neutron irradiation on carbon doped MgB2 wire segments

NASA Astrophysics Data System (ADS)

Wilke, R. H. T.; Bud'ko, S. L.; Canfield, P. C.; Finnemore, D. K.; Suplinskas, Raymond J.; Farmer, J.; Hannahs, S. T.

2006-06-01

We have studied the evolution of superconducting and normal state properties of neutron irradiated Mg(B0.962C0.038)2 wire segments as a function of post-exposure annealing time and temperature. The initial fluence fully suppressed superconductivity and resulted in an anisotropic expansion of the unit cell. Superconductivity was restored by post-exposure annealing. The upper critical field, Hc2(T = 0), approximately scales with Tc, starting with an undamaged Tc near 37 K and Hc2(T = 0) near 32 T. Up to an annealing temperature of 400 °C the recovery of Tc tends to coincide with a decrease in the normal state resistivity and a systematic recovery of the lattice parameters. Above 400 °C a decrease in ordering along the c-direction coincides with an increase in resistivity, but no apparent change in the evolution of Tc and Hc2. To a first order approximation, it appears that carbon doping and neutron damage affect the superconducting properties of MgB2 independently.

Investigation of high dielectric constant ceramics and films with improved temperature stability of doped and undoped lead indium niobate:lead magnesium niobate

NASA Astrophysics Data System (ADS)

Tai, Cheuk Wai

Complex perovskite-structured relaxor ferroelectric ceramics of (x)Pb(In 1/2Nb1/2)O3:(1-x)Pb(Mg 1/3Nb2/3)O3 with x = 0.1 to 0.9 were studied extensively during the project. The ceramics were fabricated by conventional mixed oxide route of the two-step method. Measurements of their dielectric properties and ferroelectric hysteresis were performed to explore their potential for capacitor applications. The results show many features common to the relaxor behavior, including slim ferroelectric hysteresis loop and frequency dispersions in plots of relative permittivity. In addition, the ceramics with x = 0.3 to 0.7 show relative permittivity that is highly stable over the temperature range -30°C to 125°C. In order to explore structural alterations and their subsequent influence on dielectric properties, a variety of dopants were added to (0.3)Pb(In 1/2Nb1/2)O3:(0.7)Pb(Mg1/3Nb2/3 )O3 ceramics. The additives were Ba2+, Sr 2+, La3+, Na+, Ti4+ and Yb4+ obtained from different raw materials of oxides or carbonates. The modified ceramics were also fabricated by the two-step method. Fourteen ceramics samples doped with 2 or 5 mole % of the above elements, 5 mole % Na + 2 mole % Ti and 5 mole % Na + 5 mole % Ti doped were characterized in total. The measured dielectric properties of these ceramics were different to those of the parent ceramics and some of these meet the EIA-standard for industrial ceramic capacitor applications. An exploratory fabrication and study of thin films of the (0.4)Pb(In 1/2Nb1/2)O3:(0.6)Pb(Mg1/3Nb2/3 )O3 and two doped (0.3)Pb(In1/2Nb1/2)O 3: (0.7)Pb(Mg1/3Nb2/3)O3 compositions were carried out to demonstrate their potential for MEMS or other micro- or nano-scale systems. The epitaxial films were grown successfully by pulsed laser deposition (PLD). Prior to deposition of the films, La0.7Sr 0.3MnO3 (LSMO) bottom electrode was first grown on LaAlO 3 substrate. The orientation relationship between film, electrode and substrate was characterized by x-ray diffraction. The dielectric properties and the ferroelectric hysteresis loops of the films were measured. (Abstract shortened by UMI.)

Modulation of Jahn-Teller effect on magnetization and spontaneous electric polarization of CuFeO2

NASA Astrophysics Data System (ADS)

Xiao, Guiling; Xia, Zhengcai; Wei, Meng; Huang, Sha; Shi, Liran; Zhang, Xiaoxing; Wu, Huan; Yang, Feng; Song, Yujie; Ouyang, Zhongwen

2018-03-01

CuFe0.99Mn0.01O2 and CuFe0.99Co0.01O2 single crystal samples are grown by a floating zone technique and their magnetization and spontaneous electric polarization have been investigated. Similarly with pure CuFeO2, an obviously anisotropic magnetization and spontaneous electric polarization were observed in the both doped samples, and their phase transition critical fields and temperatures are directly doping ion dependent. Considering the different d-shell configuration and ionic size between Mn3+, Co3+ and Fe3+ ions, in which the Mn3+ ion with Jahn-Teller (J-T) effect has different distortion on the geometry frustration from both of Fe3+ and Co3+ ion. Since for Mn3+ ion, the orbital splitting results from the low-symmetry J-T distortion in a crystal-field environment leads to a distorted MnO6 octahedron, which different from undistorted FeO6 and CoO6 octahedrons. The strain between distorted and undistorted octahedrons produces different effects on the spin reorientation transition and spontaneous electric polarization. Although the pure CuFeO2 has a very strong and robust frustration, the presence of the strain due to the random distribution of distorted MnO6 octahedron and undistorted CoO6 (FeO6) octahedrons leads to its spin reorientation transitions and spontaneous electric polarization different from CuFeO2.

SHI irradiation effect on pure and Mn doped ZnO thin films

NASA Astrophysics Data System (ADS)

Khawal, H. A.; Raskar, N. D.; Dole, B. N.

2017-05-01

Investigated the structural, surface, electrical and modifications induced by Swift Heavy Ions (SHI) irradiation on pure and Mn substituted ZnO thin films were observed. Thin films of Zn1-xMnxO (x = 0.00, 0.04) were synthesized using the dip coating technique. All thin films irradiated by Li3+ swift heavy ions with fluence 5 × 1013 ions/cm2. The XRD peak reveals that all the samples exhibit wurtzite structures. Surface morphology of samples was investigated by SEM, it was observed that pristine samples of ZnO thin film shows spherical shape but for 4 % Mn substituted ZnO thin film with 5 × 1013 ions/cm2 fluence, it reveals that big grain spherical morphology like structure respectively. I-V characteristics were recorded in the voltage range -5 to 5 V. All curves were passed through origin and nearly linear exhibit ohmic in nature for the films.

Effects of Co and Mn doping in K0.8Fe2-ySe2 revisited.

PubMed

Zhou, Tingting; Chen, Xiaolong; Guo, Jiangang; Jin, Shifeng; Wang, Gang; Lai, Xiaofang; Ying, Tianping; Zhang, Han; Shen, Shijie; Wang, Shunchong; Zhu, Kaixing

2013-07-10

Accumulated evidence indicates that phase separation occurs in potassium intercalated iron selenides, a superconducting phase coexisting with the antiferromagnetic phase K2Fe4Se5, the so-called '245 phase'. Here, we report a comparative study of substitution effects by Co and Mn for Fe sites in K0.8Fe2-ySe2 within the phase separation scenario. Our results demonstrate that Co and Mn dopants have distinct differences in occupancy and hence in the suppression mechanism of superconductivity upon doping of Fe sites. In K0.8Fe2-xCoxSe2, Co prefers to occupy the lattice of the superconducting phase and suppresses superconductivity very quickly, obeying the magnetic pair-breaking mechanism or the collapse of the Fermi surface nesting mechanism. In contrast, in K0.8Fe1.7-xMnxSe2, Mn shows no preferential occupancy in the superconducting phase or the 245 phase. The suppression of superconductivity can be attributed to restraining of the superconducting phase and meanwhile inducing another non-superconducting phase by Mn doping.

Structural control of polyhedral compression in synthetic braunite, Mn2+Mn3+6O8SiO4

NASA Astrophysics Data System (ADS)

Miletich, R.; Allan, D. R.; Angel, R. J.

The compression of synthetic braunite, Mn2+Mn3+6O8SiO4, was studied by high-pressure single-crystal X-ray diffraction carried out in a diamond-anvil cell. The equation of state at room temperature (third-order Birch-Murnaghan equation of state: V0=1661.15(8) Å3, K0,298=180.7+/-0.9 GPa, K'=6.5+/-0.3) was determined from unit-cell volume data to 9.18 GPa. Crystal structures were determined at 6 different pressures to 7.69 GPa. Compression of the structure (space group I41/acd) was found to be slightly anisotropic (a0=9.4262(4) Å, Ka=499+/-4 GPa, Ka'=19.7+/-0.9 c0=18.6964(6) Å, Kc=657+/-6 GPa, Kc'=15.7+/-1.4) which can be attributed to the fact that the Mn3+-O bonds, which are the most compressible bonds, are aligned closer to the (001) plane than to the c axis. The large bulk modulus is the result of the structural topology in which 2/3 and 1/2 of the edges of the Mn2+O8 and Mn3+O6 polyhedra share edges with other polyhedra. The Mn2+O8 polyhedra were found to compress isotropically, whereas anisotropic compressional behaviour was observed for all three Mn3+O6 octahedra. Although the polyhedral geometry of all three crystallographically independent Mn3+ sites shows the same type of uniaxially elongated distortion, the compression of the individual octahedral configurations was found to be strongly dependent upon both the geometry of the polyhedron itself and the types of, and the connectivity to, the neighbouring polyhedra. The differences in the configuration of the different oxygen atoms, and therefore the structural topology, is one of the major factors determining the type and degree of the pressure-induced distortion, while the Jahn-Teller effect plays a subordinate role.

About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

PubMed

Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

2016-10-12

The reactivity of mixtures of high voltage spinel cathode materials Li 2 NiMn 3 O 8 , Li 2 FeMn 3 O 8 , and LiCoMnO 4 cosintered with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 and Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li 2 MnO 3 and then decompose to form stable and often insulating phases such as La 2 Zr 2 O 7 , La 2 O 3 , La 3 TaO 7 , TiO 2 , and LaMnO 3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 mixtures, the Mn tends to oxidize to MnO 2 or Mn 2 O 3 , supplying lithium to the electrolyte for the formation of Li 3 PO 4 and metal phosphates such as AlPO 4 and LiMPO 4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

Above room temperature ferromagnetism in Si:Mn and TiO(2-delta)Co.

PubMed

Granovsky, A; Orlov, A; Perov, N; Gan'shina, E; Semisalova, A; Balagurov, L; Kulemanov, I; Sapelkin, A; Rogalev, A; Smekhova, A

2012-09-01

We present recent experimental results on the structural, electrical, magnetic, and magneto-optical properties of Mn-implanted Si and Co-doped TiO(2-delta) magnetic oxides. Si wafers, both n- and p-type, with high and low resistivity, were used as the starting materials for implantation with Mn ions at the fluencies up to 5 x 10(16) cm(-2). The saturation magnetization was found to show the lack of any regular dependence on the Si conductivity type, type of impurity and the short post-implantation annealing. According to XMCD Mn impurity in Si does not bear any appreciable magnetic moment at room temperature. The obtained results indicate that above room temperature ferromagnetism in Mn-implanted Si originates not from Mn impurity but rather from structural defects in Si. The TiO(2-delta):Co thin films were deposited on LaAlO3 (001) substrates by magnetron sputtering in the argon-oxygen atmosphere at oxygen partial pressure of 2 x 10(-6)-2 x 10(-4) Torr. The obtained transverse Kerr effect spectra at the visible and XMCD spectra indicate on intrinsic room temperature ferromagnetism in TiO(2-delta):Co thin films at low (< 1%) volume fraction of Co.